1574 lines
173 KiB
XML
1574 lines
173 KiB
XML
<document id="5A8F602CB6F564FE6B5B82D7D75F3EA6" ID-DOI="10.1016/j.phytochem.2014.08.018" ID-ISSN="1873-3700" ID-Zenodo-Dep="10491066" IM.bibliography_approvedBy="felipe" IM.illustrations_approvedBy="carolina" IM.materialsCitations_approvedBy="felipe" IM.metadata_approvedBy="felipe" IM.tables_approvedBy="carolina" IM.taxonomicNames_approvedBy="felipe" IM.treatments_approvedBy="carolina" checkinTime="1704964522668" checkinUser="felipe" docAuthor="Malagòn, Omar, Porta, Alessio, Clericuzio, Marco, Gilardoni, Gianluca, Gozzini, Davide & Vidari, Giovanni" docDate="2014" docId="03A9878CDF173F42A5503A08FCDEFCF1" docLanguage="en" docName="Phytochemistry.107.126-134.pdf" docOrigin="Phytochemistry 107" docSource="http://dx.doi.org/10.1016/j.phytochem.2014.08.018" docStyle="DocumentStyle:9E596C34F4E94307D29315B03ACE1007.6:Phytochemistry.2014-2019.journal_article" docStyleId="9E596C34F4E94307D29315B03ACE1007" docStyleName="Phytochemistry.2014-2019.journal_article" docStyleVersion="6" docTitle="Russula nobilis" docType="treatment" docVersion="1" lastPageNumber="132" masterDocId="FF90FFF4DF163F44A5223F25FF8EFFDE" masterDocTitle="Structures and biological significance of lactarane sesquiterpenes from the European mushroom Russula nobilis" masterLastPageNumber="134" masterPageNumber="126" pageNumber="127" updateTime="1706188630851" updateUser="carolina">
|
||
<mods:mods id="4B40C220566F6A4282E52EA9D5573747" xmlns:mods="http://www.loc.gov/mods/v3">
|
||
<mods:titleInfo id="F5BFE44EED1C6B68513805BBE24764E5">
|
||
<mods:title id="9B001364F3E694AFA52990759F8569E1">Structures and biological significance of lactarane sesquiterpenes from the European mushroom Russula nobilis</mods:title>
|
||
</mods:titleInfo>
|
||
<mods:name id="DF2EE19FF442F8695A1CCC71261875AD" type="personal">
|
||
<mods:role id="8C6A1D5082050CC15B7CD5911237919E">
|
||
<mods:roleTerm id="9DC125CD38E59CE8DD3C21A837A689AA">Author</mods:roleTerm>
|
||
</mods:role>
|
||
<mods:namePart id="D6FAFCE3918A70ED85032577EEE36DD3">Malagòn, Omar</mods:namePart>
|
||
<mods:affiliation id="6DFF4E3C3C485CB443F5890C2969AA7A">Universidad Tecnica Particular de Loja, Departamento de Química Aplicada, Loja, Ecuador</mods:affiliation>
|
||
</mods:name>
|
||
<mods:name id="52FDA96C91F73BC4ED5C08C641989ECC" type="personal">
|
||
<mods:role id="74865676956D9CF02A8DBF9CC8F06A0B">
|
||
<mods:roleTerm id="F54A8016F2A0860948C9DE4F6DAC616D">Author</mods:roleTerm>
|
||
</mods:role>
|
||
<mods:namePart id="A93BEA146271C5178206C2B86F0441C3">Porta, Alessio</mods:namePart>
|
||
</mods:name>
|
||
<mods:name id="582D0D6CDC99B9DCCDD9F95DFD88B92D" type="personal">
|
||
<mods:role id="343F3F190B4E5F8BFBE8F2E453685686">
|
||
<mods:roleTerm id="AAA779C98687A3F9D59F1E31469D455A">Author</mods:roleTerm>
|
||
</mods:role>
|
||
<mods:namePart id="35AD7DC376FEC6BF4916A734953F7E83">Clericuzio, Marco</mods:namePart>
|
||
</mods:name>
|
||
<mods:name id="1EE83DC8635890062B6151AE327F3EC0" type="personal">
|
||
<mods:role id="3115FACA1408ABF4F4A8C67E6917A5E7">
|
||
<mods:roleTerm id="310F039CACE15CFCF4D9313EBE1E5A94">Author</mods:roleTerm>
|
||
</mods:role>
|
||
<mods:namePart id="95C3C91C55690485E3C33B321D97EF52">Gilardoni, Gianluca</mods:namePart>
|
||
</mods:name>
|
||
<mods:name id="5F30DA640B58B6A05BEC47E400288FC0" type="personal">
|
||
<mods:role id="1CC1680684E62ACEC37A56E7E7D02D29">
|
||
<mods:roleTerm id="2B9A206E5ABDE10F62F2158CC78BFB7C">Author</mods:roleTerm>
|
||
</mods:role>
|
||
<mods:namePart id="F5A292D50BC53FA6EDB47AA5A83490BD">Gozzini, Davide</mods:namePart>
|
||
</mods:name>
|
||
<mods:name id="8266C974CF1CC3648C74BD85231F623E" type="personal">
|
||
<mods:role id="FB1676E592E119638E0E98DC192FAC46">
|
||
<mods:roleTerm id="DB48E5C7F8B81E6A3F7C9133637009FA">Author</mods:roleTerm>
|
||
</mods:role>
|
||
<mods:namePart id="6836D52D9B274D820FCC660D186824A8">Vidari, Giovanni</mods:namePart>
|
||
</mods:name>
|
||
<mods:typeOfResource id="B0A18F6D69211C66115FEBFB67B2EABC">text</mods:typeOfResource>
|
||
<mods:relatedItem id="C79CD43A6F7C21D61DC74D2EFB9EB01B" type="host">
|
||
<mods:titleInfo id="24D9A23FFA1CA6F85E12155446D07291">
|
||
<mods:title id="1543879B90FE7252BD5E7CBC22333E9D">Phytochemistry</mods:title>
|
||
</mods:titleInfo>
|
||
<mods:part id="EEFDE3EAF7863008D7FA1E1FA5A859C6">
|
||
<mods:date id="4C1C71C7FEAED8634D71A1853453693B">2014</mods:date>
|
||
<mods:detail id="E79C80EFAD04DAD2F84AEE224B65447A" type="pubDate">
|
||
<mods:number id="D8798573F97EA0E3725A2424C0C4852E">2014-11-30</mods:number>
|
||
</mods:detail>
|
||
<mods:detail id="CEEE039718AB31F878E1F6C4C4FE2E89" type="volume">
|
||
<mods:number id="A8316B5E25BF5D9937EFFE2E2A56F7CD">107</mods:number>
|
||
</mods:detail>
|
||
<mods:extent id="253E29D4C37DD7B840A93FF228DFDEC2" unit="page">
|
||
<mods:start id="D18711922AFC1F52F2827C1D15FBA84E">126</mods:start>
|
||
<mods:end id="2E933F1E00D3DD296B7CC4404BABDE75">134</mods:end>
|
||
</mods:extent>
|
||
</mods:part>
|
||
</mods:relatedItem>
|
||
<mods:location id="09DFC913332BA590A7EF80E2CA81AC64">
|
||
<mods:url id="7AA2DF3C15A9AD8F5691513CF72CB25D">http://dx.doi.org/10.1016/j.phytochem.2014.08.018</mods:url>
|
||
</mods:location>
|
||
<mods:classification id="652B770AEA5210C3099E203432ED8CA7">journal article</mods:classification>
|
||
<mods:identifier id="8A05470C08C9BACBDA6660F4F46251CF" type="DOI">10.1016/j.phytochem.2014.08.018</mods:identifier>
|
||
<mods:identifier id="17249E5FDF83E426489DA4927482BDDA" type="ISSN">1873-3700</mods:identifier>
|
||
<mods:identifier id="69B098311CE257D41B36A1AEF9B71948" type="Zenodo-Dep">10491066</mods:identifier>
|
||
</mods:mods>
|
||
<treatment id="03A9878CDF173F42A5503A08FCDEFCF1" LSID="urn:lsid:plazi:treatment:03A9878CDF173F42A5503A08FCDEFCF1" httpUri="http://treatment.plazi.org/id/03A9878CDF173F42A5503A08FCDEFCF1" lastPageId="6" lastPageNumber="132" pageId="1" pageNumber="127">
|
||
<subSubSection id="C31A6511DF173F45A5503A08FD25FA9F" box="[114,683,1325,1345]" pageId="1" pageNumber="127" type="nomenclature">
|
||
<paragraph id="8BBF369ADF173F45A5503A08FD25FA9F" blockId="1.[114,683,1325,1345]" box="[114,683,1325,1345]" pageId="1" pageNumber="127">
|
||
<heading id="D0F781F6DF173F45A5503A08FD25FA9F" box="[114,683,1325,1345]" fontSize="36" level="2" pageId="1" pageNumber="127" reason="3">
|
||
<emphasis id="B974EA88DF173F45A5503A08FD25FA9F" box="[114,683,1325,1345]" italics="true" pageId="1" pageNumber="127">
|
||
2.2. Sesquiterpenes in damaged fruiting bodies of
|
||
<taxonomicName id="4C004D19DF173F45A7713A08FD25FA9F" ID-CoL="799HN" box="[595,683,1325,1345]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="1" pageNumber="127" phylum="Basidiomycota" rank="species" species="nobilis">R. nobilis</taxonomicName>
|
||
</emphasis>
|
||
</heading>
|
||
</paragraph>
|
||
</subSubSection>
|
||
<subSubSection id="C31A6511DF173F42A5B33A43FD23FEE7" lastPageId="6" lastPageNumber="132" pageId="1" pageNumber="127" type="description">
|
||
<paragraph id="8BBF369ADF173F45A5B33A43FAC8FDB2" blockId="1.[113,783,1382,2015]" lastBlockId="1.[831,1501,182,2012]" pageId="1" pageNumber="127">
|
||
To study the complex patterns of secondary metabolites enzymatically formed in injured fruiting bodies, freshly collected undamaged specimens of
|
||
<taxonomicName id="4C004D19DF173F45A45A3AB9FE5EFA6E" box="[376,464,1436,1456]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="1" pageNumber="127" phylum="Basidiomycota" rank="species" species="nobilis">
|
||
<emphasis id="B974EA88DF173F45A45A3AB9FE5EFA6E" box="[376,464,1436,1456]" italics="true" pageId="1" pageNumber="127">R. nobilis</emphasis>
|
||
</taxonomicName>
|
||
were finely ground at RT without adding any solvent, then left at RT in the air; subsequently, samples of the mush were extracted with
|
||
<collectingCountry id="F317760ADF173F45A4C53AF0FD8AFA36" box="[487,516,1493,1512]" name="Switzerland" pageId="1" pageNumber="127">CH</collectingCountry>
|
||
<subScript id="178434DFDF173F45A7263AFBFD83FA34" attach="both" box="[516,525,1502,1514]" fontSize="5" pageId="1" pageNumber="127">2</subScript>
|
||
Cl
|
||
<subScript id="178434DFDF173F45A7033AFBFDA4FA34" attach="left" box="[545,554,1502,1514]" fontSize="5" pageId="1" pageNumber="127">2</subScript>
|
||
at different times after injury and extracts were analyzed by TLC. Following this procedure, we observed a continuous change in the patterns of metabolites extracted in the first 30 min. Thus, to identify the compound(s) responsible for the pungency of
|
||
<taxonomicName id="4C004D19DF173F45A4E53961FDACF986" box="[455,546,1604,1624]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="1" pageNumber="127" phylum="Basidiomycota" rank="species" species="nobilis">
|
||
<emphasis id="B974EA88DF173F45A4E53961FDACF986" box="[455,546,1604,1624]" italics="true" pageId="1" pageNumber="127">R. nobilis</emphasis>
|
||
</taxonomicName>
|
||
to the human tongue, extraction of the mush had to be done within 30 s after crushing fruiting bodies. Separation of the extract on a RP-18 column afforded the antimicrobial dialdehyde (
|
||
<emphasis id="B974EA88DF173F45A4D139BCFD8AF975" box="[499,516,1689,1707]" italics="true" pageId="1" pageNumber="127">—</emphasis>
|
||
)-velleral
|
||
<emphasis id="B974EA88DF173F45A74C39BCFDF5F972" bold="true" box="[622,635,1689,1708]" pageId="1" pageNumber="127">3</emphasis>
|
||
, followed by unchanged velutinal esters. Velleral
|
||
<emphasis id="B974EA88DF173F45A4FC3991FE65F919" bold="true" box="[478,491,1716,1735]" pageId="1" pageNumber="127">3</emphasis>
|
||
is one of the acrid sesquiterpene dialdehydes responsible for the pungency of several
|
||
<taxonomicName id="4C004D19DF173F45A79A39EAFC81F93D" box="[696,783,1743,1763]" class="Agaricomycetes" family="Russulaceae" genus="Lactarius" kingdom="Fungi" order="Russulales" pageId="1" pageNumber="127" phylum="Basidiomycota" rank="genus">
|
||
<emphasis id="B974EA88DF173F45A79A39EAFC81F93D" box="[696,783,1743,1763]" italics="true" pageId="1" pageNumber="127">Lactarius</emphasis>
|
||
</taxonomicName>
|
||
and
|
||
<taxonomicName id="4C004D19DF173F45A5BE39CEFEBDF921" box="[156,307,1771,1791]" pageId="1" pageNumber="127">
|
||
<emphasis id="B974EA88DF173F45A5BE39CEFF6BF921" box="[156,229,1771,1791]" italics="true" pageId="1" pageNumber="127">Russula</emphasis>
|
||
species
|
||
</taxonomicName>
|
||
, being formed by enzymatic conversion of velutinal esters, such as the stearate (+)
|
||
<emphasis id="B974EA88DF173F45A723382CFD9CF8C5" box="[513,530,1801,1819]" italics="true" pageId="1" pageNumber="127">—</emphasis>
|
||
<emphasis id="B974EA88DF173F45A733382DFD90F8C5" bold="true" box="[529,542,1800,1819]" pageId="1" pageNumber="127">1</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF173F45A711382DFC84F8C5" author="Sterner, O. & Bergman, R. & Kihlberg, J. & Wickberg, B." box="[563,778,1800,1820]" pageId="1" pageNumber="127" pagination="279 - 288" refId="ref11685" refString="Sterner, O., Bergman, R., Kihlberg, J., Wickberg, B., 1985. The Sesquiterpenes of Lactarius vellereus and their role in a proposed chemical defense system. J. Nat. Prod. 48, 279 - 288." type="journal article" year="1985">Sterner et al., 1985</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A5533801FE0DF8E9" author="Daniewski, W. M. & Vidari, G." box="[113,387,1828,1847]" pageId="1" pageNumber="127" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
). Notably, velleral
|
||
<emphasis id="B974EA88DF173F45A71F3801FDC4F8E9" bold="true" box="[573,586,1828,1847]" pageId="1" pageNumber="127">3</emphasis>
|
||
was rapidly metabolized in damaged specimens of
|
||
<taxonomicName id="4C004D19DF173F45A49D381AFD99F88D" box="[447,535,1855,1875]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="1" pageNumber="127" phylum="Basidiomycota" rank="species" species="nobilis">
|
||
<emphasis id="B974EA88DF173F45A49D381AFD99F88D" box="[447,535,1855,1875]" italics="true" pageId="1" pageNumber="127">R. nobilis</emphasis>
|
||
</taxonomicName>
|
||
, being almost undetectable in an extract made 1 min after injury, whereas a significant amount of stearate
|
||
<emphasis id="B974EA88DF173F45A41F385DFEC4F855" bold="true" box="[317,330,1912,1931]" pageId="1" pageNumber="127">1</emphasis>
|
||
was still present. On the other hand, a TLC of an extract of
|
||
<taxonomicName id="4C004D19DF173F45A42F38B6FEEDF879" box="[269,355,1939,1959]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="1" pageNumber="127" phylum="Basidiomycota" rank="species" species="nobilis">
|
||
<emphasis id="B974EA88DF173F45A42F38B6FEEDF879" box="[269,355,1939,1959]" italics="true" pageId="1" pageNumber="127">R. nobilis</emphasis>
|
||
</taxonomicName>
|
||
made 20 min after mincing fruiting bodies indicated the absence of dialdehyde
|
||
<emphasis id="B974EA88DF173F45A4FC388AFE65F81C" bold="true" box="[478,491,1967,1986]" pageId="1" pageNumber="127">3</emphasis>
|
||
as well as stearate
|
||
<emphasis id="B974EA88DF173F45A78E388AFD37F81C" bold="true" box="[684,697,1967,1986]" pageId="1" pageNumber="127">1</emphasis>
|
||
; in their place, different more polar compounds were detected as intensely colored red–blue–green spots by staining silica gel plates with the sulphovanillin reagent. The extract was then partitioned between hexane and MeOH–H
|
||
<subScript id="178434DFDF173F45A13F3FD2FBA8FEDD" attach="both" box="[1053,1062,247,259]" fontSize="5" pageId="1" pageNumber="127">2</subScript>
|
||
O (9:1), and the components of the polar layer were subsequently separated by multiple chromatographic separations on silica gel and RP-18 columns, to give several oxygenated sesquiterpenes, namely: the known furanolactaranes furandiols (+)
|
||
<emphasis id="B974EA88DF173F45A6A03E7BFC1DFEAE" box="[898,915,350,368]" italics="true" pageId="1" pageNumber="127">—</emphasis>
|
||
<emphasis id="B974EA88DF173F45A6B03E7BFC11FEAF" bold="true" box="[914,927,350,369]" pageId="1" pageNumber="127">4</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF173F45A6933E7BFBFAFEAF" author="Nozoe, S. & Matsumoto, H. & Urano, S." box="[945,1140,350,369]" pageId="1" pageNumber="127" pagination="3125 - 3128" refId="ref11530" refString="Nozoe, S., Matsumoto, H., Urano, S., 1971. The structure of new sesquiterpenes from basidiomycetes. Tetrahedron Lett., 3125 - 3128." type="book chapter" year="1971">Nozoe et al., 1971</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A1A13E7BFA2BFEAF" author="Daniewski, W. M. & Vidari, G." box="[1155,1445,350,369]" pageId="1" pageNumber="127" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
) and (+)
|
||
<emphasis id="B974EA88DF173F45A6793E5FFCE2FE52" box="[859,876,378,396]" italics="true" pageId="1" pageNumber="127">—</emphasis>
|
||
<emphasis id="B974EA88DF173F45A64E3E5FFCF7FE53" bold="true" box="[876,889,378,397]" pageId="1" pageNumber="127">5</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF173F45A6A43E5FFBC6FE53" author="Sterner, O. & Wik, O. & Carter, R. E." box="[902,1096,377,397]" pageId="1" pageNumber="127" pagination="43 - 47" refId="ref11734" refString="Sterner, O., Wik, O., Carter, R. E., 1988. The structure of a novel fungal sesquiterpene elucidated by spectral methods. Acta Chem. Scand. B 42, 43 - 47." type="journal article" year="1988">Sterner et al., 1988</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A1733E5CFAE8FE53" author="Daniewski, W. M. & Vidari, G." box="[1105,1382,377,397]" pageId="1" pageNumber="127" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
); the 5-lactaranolides epoxylactone (+)
|
||
<emphasis id="B974EA88DF173F45A17F3EB3FBE0FE76" box="[1117,1134,406,424]" italics="true" pageId="1" pageNumber="127">—</emphasis>
|
||
<emphasis id="B974EA88DF173F45A14C3EB0FBF5FE76" bold="true" box="[1134,1147,405,424]" pageId="1" pageNumber="127">6</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF173F45A1AA3EB0FAE7FE77" author="Daniewski, W. M. & Gumulka, M. & Pankowska, E. & Ptaszynska, K. & Bloszyk, E. & Jacobsson, U. & Norin, T." box="[1160,1385,405,425]" pageId="1" pageNumber="127" pagination="1499 - 1503" refId="ref10341" refString="Daniewski, W. M., Gumulka, M., Pankowska, E., Ptaszynska, K., Bloszyk, E., Jacobsson, U., Norin, T., 1993. 3,8 - Ethers of lactarane sesquiterpenes. Phytochem 32, 1499 - 1503." type="journal article" year="1993">Daniewski et al., 1993</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A0513EB0FC6AFE1A" author="Daniewski, W. M. & Vidari, G." pageId="1" pageNumber="127" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
), conjugated anhydrolactarorufin A
|
||
<emphasis id="B974EA88DF173F45A06F3E94FAFDFE1A" bold="true" box="[1357,1395,433,452]" pageId="1" pageNumber="127">7a (</emphasis>
|
||
<bibRefCitation id="EF914B6BDF173F45A0513E94FC3CFE3E" author="Daniewski, W. M. & Kroszczynski, W. & Wawrzun, A. & Rymkiewicz, A." pageId="1" pageNumber="127" pagination="2915 - 2920" refId="ref10282" refString="Daniewski, W. M., Kroszczynski, W., Wawrzun, A., Rymkiewicz, A., 1984. Constituents of higher fungi. Part XVI. Identification of Lactarius species by HPLC using sesquiterpene monohydroxylactone contents as characteristic chemotaxonomic features. J. Liquid. Chrom. 7, 2915 - 2920." type="journal article" year="1984">Daniewski et al., 1984</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A69E3EE8FB5DFE3E" author="Daniewski, W. M. & Vidari, G." box="[956,1235,461,480]" pageId="1" pageNumber="127" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
), and lactarorufin A (+)
|
||
<emphasis id="B974EA88DF173F45A09D3EEBFA5EFE3E" box="[1471,1488,462,480]" italics="true" pageId="1" pageNumber="127">—</emphasis>
|
||
<emphasis id="B974EA88DF173F45A0ED3EE8FA52FE3E" bold="true" box="[1487,1500,461,480]" pageId="1" pageNumber="127">8</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF173F45A6653ECCFBE2FE22" author="Daniewski, W. M. & Kocor, M." box="[839,1132,489,508]" pageId="1" pageNumber="127" pagination="553 - 561" refId="ref10191" refString="Daniewski, W. M., Kocor, M., 1971. Constituents of higher fungi. II. Structure of lactarorufin A .. Bull. Acad. Polon. Sci., Ser. Sci. Chim. 19, 553 - 561." type="journal article" year="1971">Daniewski and Kocor, 1971</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A15E3ECCFA2FFE22" author="Daniewski, W. M. & Vidari, G." box="[1148,1441,489,508]" pageId="1" pageNumber="127" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
); the 8,9-seco-5-lactaranolides blennin C
|
||
<emphasis id="B974EA88DF173F45A19E3D20FB75FDC6" bold="true" box="[1212,1275,517,536]" pageId="1" pageNumber="127">
|
||
(
|
||
<emphasis id="B974EA88DF173F45A1E63D23FB5BFDC6" bold="true" box="[1220,1237,518,536]" italics="true" pageId="1" pageNumber="127">—</emphasis>
|
||
)
|
||
<emphasis id="B974EA88DF173F45A1FF3D23FB60FDC6" bold="true" box="[1245,1262,518,536]" italics="true" pageId="1" pageNumber="127">—</emphasis>
|
||
9
|
||
</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF173F45A0323D20FA57FDC6" author="Vidari, G. & De Bernardi, M. & Vita-Finzi, P. & Fronza, G." box="[1296,1497,517,536]" pageId="1" pageNumber="127" pagination="1953 - 1955" refId="ref11889" refString="Vidari, G., De Bernardi, M., Vita-Finzi, P., Fronza, G., 1976. Sesquiterpenes from Lactarius blennius. Phytochem 15, 1953 - 1955." type="journal article" year="1976">Vidari et al., 1976</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A61D3D04FBD1FDEA" author="Daniewski, W. M. & Vidari, G." box="[831,1119,545,564]" pageId="1" pageNumber="127" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
) and aldehydolactone
|
||
<emphasis id="B974EA88DF173F45A06D3D04FA17FDEA" bold="true" box="[1359,1433,545,564]" pageId="1" pageNumber="127">
|
||
(
|
||
<emphasis id="B974EA88DF173F45A0753D04FAE6FDED" bold="true" box="[1367,1384,545,563]" italics="true" pageId="1" pageNumber="127">—</emphasis>
|
||
)
|
||
<emphasis id="B974EA88DF173F45A0523D04FA0FFDED" bold="true" box="[1392,1409,545,563]" italics="true" pageId="1" pageNumber="127">—</emphasis>
|
||
10
|
||
</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF173F45A08E3D04FC3FFD8E" author="Pang, Z. & Bocchio, F. & Sterner, O." pageId="1" pageNumber="127" pagination="6863 - 6866" refId="ref11563" refString="Pang, Z., Bocchio, F., Sterner, O., 1992. The isolation of new sesquiterpene aldehydes from injured fruit bodies of Lactarius scrobiculatus. Tetrahedron Lett. 33, 6863 - 6866." type="journal article" year="1992">Pang et al., 1992</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A6993D18FB5EFD8E" author="Daniewski, W. M. & Vidari, G." box="[955,1232,573,592]" pageId="1" pageNumber="127" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
); three new lactarane sesquiterpenoids,
|
||
<emphasis id="B974EA88DF173F45A6F43D7CFB9BFDB2" bold="true" box="[982,1045,601,620]" pageId="1" pageNumber="127">12–14</emphasis>
|
||
, named russulanobilines A–C.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF173F45A67C3D50FAD7FAEC" blockId="1.[831,1501,182,2012]" pageId="1" pageNumber="127">
|
||
NMR data indicated the structure of conjugated anhydrolactarorufin A for compound
|
||
<emphasis id="B974EA88DF173F45A1103DB4FBC5FD7A" bold="true" box="[1074,1099,657,676]" pageId="1" pageNumber="127">7a</emphasis>
|
||
, which was reported to occur in several
|
||
<taxonomicName id="4C004D19DF173F45A61D3D89FC66FD1E" box="[831,1000,684,704]" pageId="1" pageNumber="127">
|
||
<emphasis id="B974EA88DF173F45A61D3D89FC18FD1E" box="[831,918,684,704]" italics="true" pageId="1" pageNumber="127">Lactarius</emphasis>
|
||
species
|
||
</taxonomicName>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF173F45A6D93D88FB67FD1F" author="Daniewski, W. M. & Kroszczynski, W. & Wawrzun, A. & Rymkiewicz, A." box="[1019,1257,685,705]" pageId="1" pageNumber="127" pagination="2915 - 2920" refId="ref10282" refString="Daniewski, W. M., Kroszczynski, W., Wawrzun, A., Rymkiewicz, A., 1984. Constituents of higher fungi. Part XVI. Identification of Lactarius species by HPLC using sesquiterpene monohydroxylactone contents as characteristic chemotaxonomic features. J. Liquid. Chrom. 7, 2915 - 2920." type="journal article" year="1984">Daniewski et al., 1984</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A1D53D88FCFCFD03" author="Daniewski, W. M. & Vidari, G." pageId="1" pageNumber="127" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
); however, no physical or spectral data of an isolated sample of this sesquiterpene alcohol have been published so far (
|
||
<bibRefCitation id="EF914B6BDF173F45A0BD3DC3FB91FCC8" author="Vidari, G. & Vita-Finzi, P." pageId="1" pageNumber="127" pagination="152 - 206" refId="ref11924" refString="Vidari, G., Vita-Finzi, P., 1995. Sesquiterpenes and other secondary metabolites of the genus Lactarius (Basidiomycetes): chemistry and biological activity. In: Atta-ur-Rahman (Ed.), Studies in natural product chemistry structure and chemistry, vol. 17. Elsevier, Amsterdam, pp. 152 - 206." type="book chapter" year="1995">Vidari and Vita-Finzi, 1995</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A1103C26FAE8FCC8" author="Daniewski, W. M. & Vidari, G." box="[1074,1382,771,790]" pageId="1" pageNumber="127" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A05A3C26FC3CFCEC" author="Clericuzio, M. & Gilardoni, G. & Malagon, O. & Vidari, G. & Vita-Finzi, P." pageId="1" pageNumber="127" pagination="951 - 974" refId="ref10051" refString="Clericuzio, M., Gilardoni, G., Malagon, O., Vidari, G., Vita-Finzi, P., 2008. Sesquiterpenes of Lactarius and Russula (mushrooms): an update. Nat. Prod. Commun. 3, 951 - 974." type="journal article" year="2008">Clericuzio et al., 2008</bibRefCitation>
|
||
). Therefore, we report now the spectroscopic data of compound
|
||
<emphasis id="B974EA88DF173F45A6963C19FC42FC91" bold="true" box="[948,972,828,847]" pageId="1" pageNumber="127">7a</emphasis>
|
||
, along with its absolute configuration. In addition to three singlets attributable to the three characteristic methyl groups of the lactarane skeleton, one of which was located on a double bond (
|
||
<emphasis id="B974EA88DF173F45A6E83CB4FC5BFC7A" box="[970,981,913,932]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A6F73CBFFC6FFC78" attach="left" box="[981,993,922,934]" fontSize="5" pageId="1" pageNumber="127">H</subScript>
|
||
1.93, Me-12), the
|
||
<superScript id="7C759BD2DF173F45A1B53CA8FB2EFC47" attach="right" box="[1175,1184,909,921]" fontSize="5" pageId="1" pageNumber="127">1</superScript>
|
||
H NMR spectrum showed these characteristic resonances for structure
|
||
<emphasis id="B974EA88DF173F45A1E53C88FB51FC1E" bold="true" box="[1223,1247,941,960]" pageId="1" pageNumber="127">7a</emphasis>
|
||
: an isolated olefinic proton at
|
||
<emphasis id="B974EA88DF173F45A6A13CEFFC00FC03" box="[899,910,970,989]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A6AC3CF6FC14FC01" attach="left" box="[910,922,979,991]" fontSize="5" pageId="1" pageNumber="127">H</subScript>
|
||
5.93 assigned to H-4, an AB system collapsed at
|
||
<emphasis id="B974EA88DF173F45A0B13CEFFA10FC03" box="[1427,1438,970,989]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A0BF3CF6FA27FC01" attach="left" box="[1437,1449,979,991]" fontSize="5" pageId="1" pageNumber="127">H</subScript>
|
||
4.85 attributable to H
|
||
<subScript id="178434DFDF173F45A6CE3CCAFC7BFC25" attach="right" box="[1004,1013,1007,1019]" fontSize="5" pageId="1" pageNumber="127">2</subScript>
|
||
-13, one proton doublet (
|
||
<emphasis id="B974EA88DF173F45A1DE3CC0FA8DFC27" box="[1276,1283,997,1017]" italics="true" pageId="1" pageNumber="127">J</emphasis>
|
||
= 10.8 Hz) at
|
||
<emphasis id="B974EA88DF173F45A0B33CC3FA12FC27" box="[1425,1436,998,1017]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A0BE3CCAFA26FC25" attach="left" box="[1436,1448,1007,1019]" fontSize="5" pageId="1" pageNumber="127">H</subScript>
|
||
4.44 assignable to H-8,
|
||
<emphasis id="B974EA88DF173F45A1223B24FBBFFBCB" box="[1024,1073,1025,1045]" italics="true" pageId="1" pageNumber="127">trans</emphasis>
|
||
to H-9, two multiplets at
|
||
<subScript id="178434DFDF173F45A0653B26FAD0FBC6" attach="left" box="[1351,1374,1027,1048]" fontSize="5" pageId="1" pageNumber="127">δH</subScript>
|
||
2.78 and at
|
||
<emphasis id="B974EA88DF173F45A61D3B3AFCC4FBEC" box="[831,842,1055,1074]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A6683B0DFCD8FBEA" attach="left" box="[842,854,1064,1076]" fontSize="5" pageId="1" pageNumber="127">H</subScript>
|
||
2.30 attributed to H-2 and H-9, respectively; a triplet (
|
||
<emphasis id="B974EA88DF173F45A6653B1FFCC0FB90" box="[839,846,1082,1102]" italics="true" pageId="1" pageNumber="127">J</emphasis>
|
||
= 12.5 Hz) at
|
||
<emphasis id="B974EA88DF173F45A6CA3B19FC7DFB91" box="[1000,1011,1084,1103]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A6D13B60FC71FB8F" attach="left" box="[1011,1023,1093,1105]" fontSize="5" pageId="1" pageNumber="127">H</subScript>
|
||
1.44 along with a coupled double-doublet (
|
||
<emphasis id="B974EA88DF173F45A6653B72FCC0FBB5" box="[839,846,1111,1131]" italics="true" pageId="1" pageNumber="127">J</emphasis>
|
||
= 12.5 and 6.2 Hz) at
|
||
<emphasis id="B974EA88DF173F45A10A3B7DFBBDFBB5" box="[1064,1075,1112,1131]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A1113B44FBB1FBB3" attach="left" box="[1075,1087,1121,1133]" fontSize="5" pageId="1" pageNumber="127">H</subScript>
|
||
2.02, assigned to H
|
||
<subScript id="178434DFDF173F45A0213B44FA82FBB3" attach="left" box="[1283,1292,1121,1133]" fontSize="5" pageId="1" pageNumber="127">2</subScript>
|
||
-1; a double-doublet (
|
||
<emphasis id="B974EA88DF173F45A6653B56FCC0FB59" box="[839,846,1139,1159]" italics="true" pageId="1" pageNumber="127">J</emphasis>
|
||
= 14.0 and 7.2 Hz) at
|
||
<emphasis id="B974EA88DF173F45A10E3B50FBB9FB56" box="[1068,1079,1141,1160]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A1153B5BFBCDFB54" attach="left" box="[1079,1091,1150,1162]" fontSize="5" pageId="1" pageNumber="127">H</subScript>
|
||
1.73, along with a coupled double-doublet (
|
||
<emphasis id="B974EA88DF173F45A6543BB5FCF3FB7A" box="[886,893,1168,1188]" italics="true" pageId="1" pageNumber="127">J</emphasis>
|
||
= 14.0 and 2.2 Hz) at
|
||
<emphasis id="B974EA88DF173F45A1423BB4FBE5FB7A" box="[1120,1131,1169,1188]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A1493BBFFBF9FB78" attach="left" box="[1131,1143,1178,1190]" fontSize="5" pageId="1" pageNumber="127">H</subScript>
|
||
1.88, assignable to H
|
||
<subScript id="178434DFDF173F45A0743BBFFAD1FB78" attach="left" box="[1366,1375,1178,1190]" fontSize="5" pageId="1" pageNumber="127">2</subScript>
|
||
-10. The
|
||
<superScript id="7C759BD2DF173F45A09E3BA8FA41FB47" attach="right" box="[1468,1487,1165,1177]" fontSize="5" pageId="1" pageNumber="127">13</superScript>
|
||
C NMR spectrum (
|
||
<tableCitation id="C6820321DF173F45A6C83B88FBB9FB1E" box="[1002,1079,1197,1216]" captionStart="Table 1" captionStartId="2.[87,131,183,197]" captionText="Table 1 Experimental (75.47 MHz, CD Cl) 13C NMR resonances (δ) for compound 7a and russulanobilines A–C, and calculated 13C NMR resonances (δ) for structures 13a, 14oia, 14ƥa, 2 2 C C 15oia, and 15ƥa." pageId="1" pageNumber="127">Table 1</tableCitation>
|
||
) was fully consistent with structure
|
||
<emphasis id="B974EA88DF173F45A09C3B88FA59FB1E" bold="true" box="[1470,1495,1197,1216]" pageId="1" pageNumber="127">7a</emphasis>
|
||
. Moreover
|
||
<emphasis id="B974EA88DF173F45A6853BEFFC31FB03" bold="true" box="[935,959,1226,1245]" pageId="1" pageNumber="127">7a</emphasis>
|
||
was converted by standard acetylation conditions to
|
||
<emphasis id="B974EA88DF173F45A61D3BC3FCD7FB27" bold="true" box="[831,857,1254,1273]" pageId="1" pageNumber="127">7b</emphasis>
|
||
, which was identical, including the optical rotation, with the dehydration product of the very well-known (+)-lactarorufin A -
|
||
<emphasis id="B974EA88DF173F45A0ED3A27FA52FACB" bold="true" box="[1487,1500,1282,1301]" pageId="1" pageNumber="127">8</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF173F45A6653A3AFBD1FAEC" author="Daniewski, W. M. & Kocor, M." box="[839,1119,1311,1330]" pageId="1" pageNumber="127" pagination="585 - 593" refId="ref10145" refString="Daniewski, W. M., Kocor, M., 1970. Isolation and structure of some new sesquiterpenes from Lactarius rufus .. Bull. Acad. Polon. Sci., Ser. Sci. Chim. 18, 585 - 593." type="journal article" year="1970">Daniewski and Kocor, 1970</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A1493A3AFAC2FAEC" author="Daniewski, W. M. & Kocor, M. & Krol, J." box="[1131,1356,1311,1330]" pageId="1" pageNumber="127" pagination="2095 - 2100" refId="ref10238" refString="Daniewski, W. M., Kocor, M., Krol, J., 1976. Constituents of higher fungi. Part VII. Lactarorufin N and revised structures of lactarorufins. Roczniki Chem. 50, 2095 - 2100." type="journal article" year="1976">Daniewski et al., 1976</bibRefCitation>
|
||
).
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF173F45A67C3A1EFC64F98B" blockId="1.[831,1501,182,2012]" pageId="1" pageNumber="127">
|
||
As to the new compounds
|
||
<emphasis id="B974EA88DF173F45A1453A1EFB28FA90" bold="true" box="[1127,1190,1339,1358]" pageId="1" pageNumber="127">12–14</emphasis>
|
||
, biogenetic considerations and the presence of three characteristic methyl signals in the NMR spectra, two of which geminal to a quaternary sp
|
||
<superScript id="7C759BD2DF173F45A01C3A54FAC9FAA3" attach="left" box="[1342,1351,1393,1405]" fontSize="5" pageId="1" pageNumber="127">3</superScript>
|
||
carbon (C-11) and the third one bonded to a methine (C-3), clearly suggested they were lactarane derivatives (
|
||
<bibRefCitation id="EF914B6BDF173F45A18E3A95FA56FA1D" author="Vidari, G. & Vita-Finzi, P." box="[1196,1496,1456,1475]" pageId="1" pageNumber="127" pagination="152 - 206" refId="ref11924" refString="Vidari, G., Vita-Finzi, P., 1995. Sesquiterpenes and other secondary metabolites of the genus Lactarius (Basidiomycetes): chemistry and biological activity. In: Atta-ur-Rahman (Ed.), Studies in natural product chemistry structure and chemistry, vol. 17. Elsevier, Amsterdam, pp. 152 - 206." type="book chapter" year="1995">Vidari and Vita-Finzi, 1995</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A61D3AE8FBEEFA3E" author="Daniewski, W. M. & Vidari, G." box="[831,1120,1485,1504]" pageId="1" pageNumber="127" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A14E3AE8FAC2FA3E" author="Clericuzio, M. & Gilardoni, G. & Malagon, O. & Vidari, G. & Vita-Finzi, P." box="[1132,1356,1485,1504]" pageId="1" pageNumber="127" pagination="951 - 974" refId="ref10051" refString="Clericuzio, M., Gilardoni, G., Malagon, O., Vidari, G., Vita-Finzi, P., 2008. Sesquiterpenes of Lactarius and Russula (mushrooms): an update. Nat. Prod. Commun. 3, 951 - 974." type="journal article" year="2008">Clericuzio et al., 2008</bibRefCitation>
|
||
). Moreover, a strong band at about
|
||
<quantity id="4CF89B7FDF173F45A1003ACFFB37FA20" box="[1058,1209,1514,1534]" metricMagnitude="1" metricUnit="m" metricValue="1.755" metricValueMax="1.77" metricValueMin="1.7399999999999998" pageId="1" pageNumber="127" unit="cm" value="1755.0" valueMax="1770.0" valueMin="1740.0">1740–1770 cm</quantity>
|
||
<superScript id="7C759BD2DF173F45A19A3AC2FB43FA2C" attach="left" box="[1208,1229,1510,1523]" fontSize="5" pageId="1" pageNumber="127">
|
||
<emphasis id="B974EA88DF173F45A19A3AC2FB4AFA2D" box="[1208,1220,1511,1523]" italics="true" pageId="1" pageNumber="127">—</emphasis>
|
||
<quantity id="4CF89B7FDF173F45A1E63AC3FB43FA2C" box="[1220,1229,1510,1522]" metricMagnitude="-2" metricUnit="m" metricValue="2.54" pageId="1" pageNumber="127" unit="in" value="1.0">1</quantity>
|
||
</superScript>
|
||
in the IR spectra and the signal for an ester carbonyl group at
|
||
<emphasis id="B974EA88DF173F45A1E6392DFB41F9C5" box="[1220,1231,1544,1563]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A1ED3934FB57F9C3" attach="left" box="[1231,1241,1553,1565]" fontSize="5" pageId="1" pageNumber="127">C</subScript>
|
||
170–175 ppm in the
|
||
<superScript id="7C759BD2DF173F45A09E3921FA41F9CE" attach="right" box="[1468,1487,1540,1552]" fontSize="5" pageId="1" pageNumber="127">13</superScript>
|
||
C NMR spectra indicated that all the three compounds were unsaturated Ƴ- lactones.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF173F46A67C397BFF33F990" blockId="1.[831,1501,182,2012]" lastBlockId="2.[87,757,1176,1614]" lastPageId="2" lastPageNumber="128" pageId="1" pageNumber="127">
|
||
The structure of russulanobiline A
|
||
<emphasis id="B974EA88DF173F45A19D397BFB56F9AF" bold="true" box="[1215,1240,1630,1649]" pageId="1" pageNumber="127">12</emphasis>
|
||
was derived by comparison with that of vellerolactone
|
||
<emphasis id="B974EA88DF173F45A159395FFB1AF953" bold="true" box="[1147,1172,1658,1677]" pageId="1" pageNumber="127">11</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF173F45A181395FFA57F953" author="Froborg, J. & Magnusson, G." box="[1187,1497,1658,1677]" pageId="1" pageNumber="127" pagination="6728 - 6733" refId="ref11159" refString="Froborg, J., Magnusson, G., 1978. Fungal Extractives. 12. Construction of the vellerane skeleton with total syntheses of racemic velleral, vellerolactone, and pyrovellerolactone. Revised structures .. J. Amer. Chem. Soc. 100, 6728 - 6733." type="journal article" year="1978">Froborg and Magnusson, 1978</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF173F45A61D39B3FBD0F977" author="Daniewski, W. M. & Vidari, G." box="[831,1118,1686,1705]" pageId="1" pageNumber="127" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
). In fact, in analogy with compound
|
||
<emphasis id="B974EA88DF173F45A61D3997FCD6F91B" bold="true" box="[831,856,1714,1733]" pageId="1" pageNumber="127">11</emphasis>
|
||
, the
|
||
<superScript id="7C759BD2DF173F45A6AF398BFC18F964" attach="right" box="[909,918,1710,1722]" fontSize="5" pageId="1" pageNumber="127">1</superScript>
|
||
H NMR spectrum of
|
||
<emphasis id="B974EA88DF173F45A14A3997FB0FF91B" bold="true" box="[1128,1153,1714,1733]" pageId="1" pageNumber="127">12</emphasis>
|
||
showed a collapsed AB system at
|
||
<emphasis id="B974EA88DF173F45A61D39EBFCC4F93F" box="[831,842,1742,1761]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A66839F2FCD8F93D" attach="left" box="[842,854,1751,1763]" fontSize="5" pageId="1" pageNumber="127">H</subScript>
|
||
4.82 for the H
|
||
<subScript id="178434DFDF173F45A6C239F2FC67F93D" attach="left" box="[992,1001,1751,1763]" fontSize="5" pageId="1" pageNumber="127">2</subScript>
|
||
-13, which was allylically coupled (
|
||
<emphasis id="B974EA88DF173F45A06739E8FAC2F93F" box="[1349,1356,1741,1761]" italics="true" pageId="1" pageNumber="127">J</emphasis>
|
||
= 1.3 Hz) with H-8 (
|
||
<emphasis id="B974EA88DF173F45A65639CFFCF1F923" box="[884,895,1770,1789]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A65D39D6FC05F921" attach="left" box="[895,907,1779,1791]" fontSize="5" pageId="1" pageNumber="127">H</subScript>
|
||
5.75); moreover, the
|
||
<superScript id="7C759BD2DF173F45A14939C3FBFAF92C" attach="right" box="[1131,1140,1766,1778]" fontSize="5" pageId="1" pageNumber="127">1</superScript>
|
||
H–
|
||
<superScript id="7C759BD2DF173F45A1B039C3FB15F92C" attach="right" box="[1170,1179,1766,1778]" fontSize="5" pageId="1" pageNumber="127">1</superScript>
|
||
H COSY spectrum indicated the entire proton spin system extending from H-4 to H
|
||
<subScript id="178434DFDF173F45A064382AFAC1F8C5" attach="left" box="[1350,1359,1807,1819]" fontSize="5" pageId="1" pageNumber="127">2</subScript>
|
||
-1 through H- 3 and H-2, with H-3 being also coupled to Me-12, as for compound
|
||
<emphasis id="B974EA88DF173F45A61D3818FCD6F88E" bold="true" box="[831,856,1853,1872]" pageId="1" pageNumber="127">11</emphasis>
|
||
. One tertiary OH group was located at the quaternary sp
|
||
<superScript id="7C759BD2DF173F45A0AB381CFA1CF89B" attach="left" box="[1417,1426,1849,1861]" fontSize="5" pageId="1" pageNumber="127">3</superScript>
|
||
carbon C-9 of
|
||
<emphasis id="B974EA88DF173F45A6A6387CFC13F8B2" bold="true" box="[900,925,1881,1900]" pageId="1" pageNumber="127">12</emphasis>
|
||
, which resonated at
|
||
<emphasis id="B974EA88DF173F45A154387CFB0FF8B2" box="[1142,1153,1881,1900]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A1A33847FB05F8B0" attach="left" box="[1153,1163,1890,1902]" fontSize="5" pageId="1" pageNumber="127">C</subScript>
|
||
83.3 (s). In accordance with this position of the OH group, in the
|
||
<superScript id="7C759BD2DF173F45A15F3854FB08F8A3" attach="right" box="[1149,1158,1905,1917]" fontSize="5" pageId="1" pageNumber="127">1</superScript>
|
||
H NMR spectrum of
|
||
<emphasis id="B974EA88DF173F45A06D3850FAE6F856" bold="true" box="[1359,1384,1909,1928]" pageId="1" pageNumber="127">12</emphasis>
|
||
H
|
||
<subScript id="178434DFDF173F45A05C385BFA09F854" attach="right" box="[1406,1415,1918,1930]" fontSize="5" pageId="1" pageNumber="127">2</subScript>
|
||
-10 gave rise to an isolated AB system (
|
||
<emphasis id="B974EA88DF173F45A14438B5FBE3F87A" box="[1126,1133,1936,1956]" italics="true" pageId="1" pageNumber="127">J</emphasis>
|
||
<subScript id="178434DFDF173F45A14E38BFFB0EF878" attach="left" box="[1132,1152,1946,1958]" fontSize="5" pageId="1" pageNumber="127">AB</subScript>
|
||
= 13.2 Hz) centered at
|
||
<emphasis id="B974EA88DF173F45A04638B4FAE1F87A" box="[1380,1391,1937,1956]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A04D38BFFAF5F878" attach="left" box="[1391,1403,1946,1958]" fontSize="5" pageId="1" pageNumber="127">H</subScript>
|
||
1.80; and the signal for H-8 (
|
||
<emphasis id="B974EA88DF173F45A6D83888FB8BF81E" box="[1018,1029,1965,1984]" italics="true" pageId="1" pageNumber="127">δ</emphasis>
|
||
<subScript id="178434DFDF173F45A1273893FB9FF81C" attach="left" box="[1029,1041,1974,1986]" fontSize="5" pageId="1" pageNumber="127">H</subScript>
|
||
5.75) showed no vicinal couplings; moreover, due to the electronegativity of the vicinal OH group, H-8 was shifted downfield in comparison with the corresponding signal (
|
||
<emphasis id="B974EA88DF143F46A7AF3BBDFD16FB75" box="[653,664,1176,1195]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A7BA3B84FD2AFB73" attach="left" box="[664,676,1185,1197]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
5.61) of 9-deoxy-lactone
|
||
<emphasis id="B974EA88DF143F46A4203B91FE95FB19" bold="true" box="[258,283,1204,1223]" pageId="2" pageNumber="128">11</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF143F46A4083B91FDDAFB19" author="Magnusson, G. & Thoren, S." box="[298,596,1204,1223]" pageId="2" pageNumber="128" pagination="1573 - 1578" refId="ref11497" refString="Magnusson, G., Thoren, S., 1973. Fungal extractives III. Two sesquiterpene lactones from Lactarius. Acta Chem. Scand. 27, 1573 - 1578." type="journal article" year="1973">Magnusson and Thorén, 1973</bibRefCitation>
|
||
). In addition, in the
|
||
<superScript id="7C759BD2DF143F46A5A23BE9FF07FB06" attach="right" box="[128,137,1228,1240]" fontSize="5" pageId="2" pageNumber="128">1</superScript>
|
||
H NMR spectrum of compound
|
||
<quantity id="4CF89B7FDF143F46A4ED3BEAFD8AFB3C" box="[463,516,1231,1250]" metricMagnitude="-1" metricUnit="m" metricValue="3.048" pageId="2" pageNumber="128" unit="in" value="12.0">
|
||
<emphasis id="B974EA88DF143F46A4ED3BEAFE66FB3C" bold="true" box="[463,488,1231,1250]" pageId="2" pageNumber="128">12</emphasis>
|
||
in
|
||
</quantity>
|
||
CD
|
||
<subScript id="178434DFDF143F46A70A3BFCFDBFFB3B" attach="both" box="[552,561,1241,1253]" fontSize="5" pageId="2" pageNumber="128">2</subScript>
|
||
Cl
|
||
<subScript id="178434DFDF143F46A7673BFCFDC0FB3B" attach="left" box="[581,590,1241,1253]" fontSize="5" pageId="2" pageNumber="128">2</subScript>
|
||
, the doublet for H
|
||
<subScript id="178434DFDF143F46A54A3BD1FFFFFADE" attach="right" box="[104,113,1268,1280]" fontSize="5" pageId="2" pageNumber="128">3</subScript>
|
||
-12 (
|
||
<emphasis id="B974EA88DF143F46A58A3BC9FF3DFB21" box="[168,179,1260,1279]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A5913BD0FF31FADF" attach="left" box="[179,191,1269,1281]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
1.31) experienced a downfield shift of 0.19 ppm in comparison with the corresponding signal for the 9-deoxy derivative
|
||
<emphasis id="B974EA88DF143F46A5A13A06FF12FAE8" bold="true" box="[131,156,1315,1334]" pageId="2" pageNumber="128">11</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF143F46A5893A01FE5BFAE8" author="Magnusson, G. & Thoren, S." box="[171,469,1315,1335]" pageId="2" pageNumber="128" pagination="1573 - 1578" refId="ref11497" refString="Magnusson, G., Thoren, S., 1973. Fungal extractives III. Two sesquiterpene lactones from Lactarius. Acta Chem. Scand. 27, 1573 - 1578." type="journal article" year="1973">Magnusson and Thorén, 1973</bibRefCitation>
|
||
), and the shift was even larger (0.33 ppm) in C
|
||
<subScript id="178434DFDF143F46A4343A6DFE91FA8A" attach="both" box="[278,287,1352,1364]" fontSize="5" pageId="2" pageNumber="128">5</subScript>
|
||
D
|
||
<specimenCount id="9D06FD13DF143F46A40D3A6DFEC1FA8C" box="[303,335,1343,1364]" count="5" pageId="2" pageNumber="128" type="generic">
|
||
<subScript id="178434DFDF143F46A40D3A6DFEB6FA8A" attach="both" box="[303,312,1352,1364]" fontSize="5" pageId="2" pageNumber="128">5</subScript>
|
||
N.
|
||
</specimenCount>
|
||
Similarly, the signals for H-2 and
|
||
<subScript id="178434DFDF143F46A7BC3A1AFD4CFA8C" attach="right" box="[670,706,1343,1365]" fontSize="7" pageId="2" pageNumber="128">Hoi-</subScript>
|
||
10 of russulanobiline A
|
||
<emphasis id="B974EA88DF143F46A43C3A7EFEB9FAB0" bold="true" box="[286,311,1371,1390]" pageId="2" pageNumber="128">12</emphasis>
|
||
experienced solvent-induced deshielding effects of 0.15 and 0.16 ppm, respectively, in C
|
||
<subScript id="178434DFDF143F46A7073AA5FDA0FA52" attach="both" box="[549,558,1408,1420]" fontSize="5" pageId="2" pageNumber="128">5</subScript>
|
||
D
|
||
<subScript id="178434DFDF143F46A71C3AA5FDC9FA52" attach="both" box="[574,583,1408,1420]" fontSize="5" pageId="2" pageNumber="128">5</subScript>
|
||
N relative to CD
|
||
<subScript id="178434DFDF143F46A7C73AA5FD7BFA52" attach="left" box="[741,757,1408,1420]" fontSize="5" pageId="2" pageNumber="128">2-</subScript>
|
||
Cl
|
||
<subScript id="178434DFDF143F46A5493AB9FFFAFA76" attach="left" box="[107,116,1436,1448]" fontSize="5" pageId="2" pageNumber="128">2</subScript>
|
||
. These solvent shifts (
|
||
<bibRefCitation id="EF914B6BDF143F46A4753AB6FDA6FA78" author="Demarco, P. & Farkas, E. & Doddrell, D. & Banavara, L. M. & Wenkert, E." box="[343,552,1427,1446]" pageId="2" pageNumber="128" pagination="5480 - 5486" refId="ref10566" refString="Demarco, P., Farkas, E., Doddrell, D., Banavara, L. M., Wenkert, E., 1968. Pyridineinduced solvent shifts in the nuclear magnetic resonance spectra of hydroxylic compounds. J. Amer. Chem. Soc. 90, 5480 - 5486." type="journal article" year="1968">Demarco et al., 1968</bibRefCitation>
|
||
) strongly suggested the
|
||
<emphasis id="B974EA88DF143F46A5A23A8BFF17FA1C" box="[128,153,1454,1474]" italics="true" pageId="2" pageNumber="128">cis</emphasis>
|
||
-stereochemistry of H
|
||
<subScript id="178434DFDF143F46A4553A9DFE0EFA1A" attach="right" box="[375,384,1464,1476]" fontSize="5" pageId="2" pageNumber="128">3</subScript>
|
||
-12, H-2 and 9-OH. The HMBC spectrum of
|
||
<emphasis id="B974EA88DF143F46A58C3AEFFF49FA03" bold="true" box="[174,199,1482,1501]" pageId="2" pageNumber="128">12</emphasis>
|
||
(
|
||
<figureCitation id="133B2A1FDF143F46A5FA3AEEFE92FA00" box="[216,284,1483,1502]" captionStart="Fig" captionStartId="2.[435,461,1999,2013]" captionTargetBox="[336,1294,1646,1967]" captionTargetId="graphics-925@2.[431,743,1681,1914]" captionTargetPageId="2" captionText="Fig. 1. Characteristic HMBC (a) and NOESY correlations (b) of russulanobiline A (12)." figureDoi="http://doi.org/10.5281/zenodo.10491070" httpUri="https://zenodo.org/record/10491070/files/figure.png" pageId="2" pageNumber="128">Fig. 1a</figureCitation>
|
||
) confirmed the connectivity of carbon atoms, while the vicinal coupling constants of H-2 and H-3, and NOESY correlations (
|
||
<figureCitation id="133B2A1FDF143F46A5C23927FEABF9CB" box="[224,293,1538,1558]" captionStart="Fig" captionStartId="2.[435,461,1999,2013]" captionTargetBox="[336,1294,1646,1967]" captionTargetId="graphics-925@2.[431,743,1681,1914]" captionTargetPageId="2" captionText="Fig. 1. Characteristic HMBC (a) and NOESY correlations (b) of russulanobiline A (12)." figureDoi="http://doi.org/10.5281/zenodo.10491070" httpUri="https://zenodo.org/record/10491070/files/figure.png" pageId="2" pageNumber="128">Fig. 1b</figureCitation>
|
||
) were fully consistent with the geometry of the calculated most stable conformer (>99%) (
|
||
<figureCitation id="133B2A1FDF143F46A700393BFDD9F9EF" box="[546,599,1566,1585]" captionStart="Fig" captionStartId="3.[148,174,633,647]" captionTargetBox="[147,751,183,601]" captionTargetId="figure-622@3.[146,751,181,604]" captionTargetPageId="3" captionText="Fig. 2. Modeled minimum energy conformation of russulanobiline A (12)." figureDoi="http://doi.org/10.5281/zenodo.10491072" httpUri="https://zenodo.org/record/10491072/files/figure.png" pageId="2" pageNumber="128">Fig. 2</figureCitation>
|
||
) of russulanobiline A
|
||
<emphasis id="B974EA88DF143F46A5BC391FFF39F993" bold="true" box="[158,183,1594,1613]" pageId="2" pageNumber="128">12</emphasis>
|
||
.
|
||
</paragraph>
|
||
<caption id="DF7F6612DF143F46A5753F92FF58FF2D" pageId="2" pageNumber="128" startId="2.[87,131,183,197]" targetType="table">
|
||
<paragraph id="8BBF369ADF143F46A5753F92FF58FF2D" blockId="2.[87,1474,183,244]" pageId="2" pageNumber="128">
|
||
<emphasis id="B974EA88DF143F46A5753F92FF1DFF1B" bold="true" box="[87,147,183,197]" pageId="2" pageNumber="128">Table 1</emphasis>
|
||
Experimental (75.47 MHz, CD Cl)
|
||
<superScript id="7C759BD2DF143F46A4483FEFFEF7FF0A" attach="right" box="[362,377,202,212]" fontSize="4" pageId="2" pageNumber="128">13</superScript>
|
||
C NMR resonances (
|
||
<emphasis id="B974EA88DF143F46A7353FE8FDAEFF02" box="[535,544,205,220]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
) for compound
|
||
<emphasis id="B974EA88DF143F46A7853FEBFD35FF02" bold="true" box="[679,699,206,220]" pageId="2" pageNumber="128">7a</emphasis>
|
||
and russulanobilines A–C, and calculated
|
||
<superScript id="7C759BD2DF143F46A1253FEFFB98FF0A" attach="right" box="[1031,1046,202,212]" fontSize="4" pageId="2" pageNumber="128">13</superScript>
|
||
C NMR resonances (
|
||
<emphasis id="B974EA88DF143F46A1963FE8FB33FF02" box="[1204,1213,205,220]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
) for structures
|
||
<emphasis id="B974EA88DF143F46A0623FE8FA4CFF02" bold="true" box="[1344,1474,203,221]" pageId="2" pageNumber="128">13a, 14oia, 14ƥa,</emphasis>
|
||
<subScript id="178434DFDF143F46A4633FF1FED1FF00" attach="right" box="[321,351,212,222]" fontSize="4" pageId="2" pageNumber="128">2 2</subScript>
|
||
<subScript id="178434DFDF143F46A7023FF1FB4BFF00" attach="left" box="[544,1221,212,222]" fontSize="4" pageId="2" pageNumber="128">C C</subScript>
|
||
<emphasis id="B974EA88DF143F46A5753FC1FFF1FF2C" bold="true" box="[87,127,226,244]" pageId="2" pageNumber="128">15oia</emphasis>
|
||
, and
|
||
<emphasis id="B974EA88DF143F46A58E3FC1FF5CFF2C" bold="true" box="[172,210,228,243]" pageId="2" pageNumber="128">15ƥa</emphasis>
|
||
.
|
||
</paragraph>
|
||
</caption>
|
||
<paragraph id="8BBF369ADF143F46A54C3E2EFAFDFC0F" pageId="2" pageNumber="128">
|
||
<table id="F900C43ADF14C0BBA54C3E22FA22FC0F" box="[110,1452,263,977]" gridcols="8" gridrows="31" pageId="2" pageNumber="128">
|
||
<tr id="353034D8DF14C0BBA54C3E22FA22FEC4" box="[110,1452,263,282]" gridrow="0" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3E22FF29FEC4" box="[110,167,263,282]" gridcol="0" gridrow="0" pageId="2" pageNumber="128">Carbon</th>
|
||
<th id="76E15DA4DF14C0BBA5E83E22FEB5FEC4" box="[202,315,263,282]" gridcol="1" gridrow="0" pageId="2" pageNumber="128">
|
||
Compound
|
||
<emphasis id="B974EA88DF143F46A40A3E2EFEB5FEC7" bold="true" box="[296,315,267,281]" pageId="2" pageNumber="128">7a</emphasis>
|
||
</th>
|
||
<th id="76E15DA4DF14C0BBA47C3E22FD9BFEC4" box="[350,533,263,282]" gridcol="2" gridrow="0" pageId="2" pageNumber="128">
|
||
Russulanobiline A (
|
||
<emphasis id="B974EA88DF143F46A4D93E2EFD81FEC7" bold="true" box="[507,527,267,281]" pageId="2" pageNumber="128">12</emphasis>
|
||
)
|
||
</th>
|
||
<th id="76E15DA4DF14C0BBA71A3E22FD61FEC4" box="[568,751,263,282]" gridcol="3" gridrow="0" pageId="2" pageNumber="128">
|
||
Russulanobiline B (
|
||
<emphasis id="B974EA88DF143F46A7F73E2EFD67FEC7" bold="true" box="[725,745,267,281]" pageId="2" pageNumber="128">13</emphasis>
|
||
)
|
||
</th>
|
||
<th id="76E15DA4DF14C0BBA6303E22FCE2FEC4" box="[786,876,263,282]" gridcol="4" gridrow="0" pageId="2" pageNumber="128">
|
||
<emphasis id="B974EA88DF143F46A6303E2EFCBBFEC7" bold="true" box="[786,821,267,281]" pageId="2" pageNumber="128">13a/</emphasis>
|
||
<emphasis id="B974EA88DF143F46A6173E2FFCC2FEC7" bold="true" box="[821,844,266,282]" pageId="2" pageNumber="128">Αδ</emphasis>
|
||
</th>
|
||
<th id="76E15DA4DF14C0BBA6AC3E22FBC2FEC4" box="[910,1100,263,282]" gridcol="5" gridrow="0" pageId="2" pageNumber="128">
|
||
Russulanobiline C (
|
||
<emphasis id="B974EA88DF143F46A1083E2EFBB0FEC7" bold="true" box="[1066,1086,267,281]" pageId="2" pageNumber="128">14</emphasis>
|
||
) a
|
||
</th>
|
||
<th id="76E15DA4DF14C0BBA14C3E22FB72FEC4" box="[1134,1276,263,282]" gridcol="6" gridrow="0" pageId="2" pageNumber="128">
|
||
<emphasis id="B974EA88DF143F46A14C3E2EFB0CFEC7" bold="true" box="[1134,1154,267,281]" pageId="2" pageNumber="128">14</emphasis>
|
||
<emphasis id="B974EA88DF143F46A1A03E2DFB12FEC7" bold="true" box="[1154,1180,264,282]" pageId="2" pageNumber="128">
|
||
<emphasis id="B974EA88DF143F46A1A03E2DFB19FEC7" bold="true" box="[1154,1175,264,282]" pageId="2" pageNumber="128">oia</emphasis>
|
||
/
|
||
</emphasis>
|
||
<emphasis id="B974EA88DF143F46A1BF3E2FFB6AFEC7" bold="true" box="[1181,1252,266,282]" pageId="2" pageNumber="128">
|
||
<emphasis id="B974EA88DF143F46A1BF3E2FFB3DFEC7" bold="true" box="[1181,1203,266,282]" pageId="2" pageNumber="128">Αδ</emphasis>
|
||
14ƥa/
|
||
</emphasis>
|
||
<emphasis id="B974EA88DF143F46A1C73E2FFB72FEC7" bold="true" box="[1253,1276,266,282]" pageId="2" pageNumber="128">Αδ</emphasis>
|
||
</th>
|
||
<th id="76E15DA4DF14C0BBA03C3E22FA22FEC4" box="[1310,1452,263,282]" gridcol="7" gridrow="0" pageId="2" pageNumber="128">
|
||
<emphasis id="B974EA88DF143F46A03C3E2EFABCFEC7" bold="true" box="[1310,1330,267,281]" pageId="2" pageNumber="128">15</emphasis>
|
||
<emphasis id="B974EA88DF143F46A0103E2DFAC2FEC7" bold="true" box="[1330,1356,264,282]" pageId="2" pageNumber="128">
|
||
<emphasis id="B974EA88DF143F46A0103E2DFAC9FEC7" bold="true" box="[1330,1351,264,282]" pageId="2" pageNumber="128">oia</emphasis>
|
||
/
|
||
</emphasis>
|
||
<emphasis id="B974EA88DF143F46A06F3E2FFA1BFEC7" bold="true" box="[1357,1429,266,282]" pageId="2" pageNumber="128">
|
||
<emphasis id="B974EA88DF143F46A06F3E2FFAEDFEC7" bold="true" box="[1357,1379,266,282]" pageId="2" pageNumber="128">Αδ</emphasis>
|
||
15ƥa/
|
||
</emphasis>
|
||
<emphasis id="B974EA88DF143F46A0B73E2FFA22FEC7" bold="true" box="[1429,1452,266,282]" pageId="2" pageNumber="128">Αδ</emphasis>
|
||
</th>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3E0DFA22FEE4" box="[110,1452,296,314]" gridrow="1" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3E0DFF29FEE4" box="[110,167,296,314]" gridcol="0" gridrow="1" pageId="2" pageNumber="128">1</th>
|
||
<td id="76E15DA4DF14C0BBA5E83E0DFEB5FEE4" box="[202,315,296,314]" gridcol="1" gridrow="1" pageId="2" pageNumber="128">48.4f</td>
|
||
<td id="76E15DA4DF14C0BBA47C3E0DFD9BFEE4" box="[350,533,296,314]" gridcol="2" gridrow="1" pageId="2" pageNumber="128">45.5</td>
|
||
<td id="76E15DA4DF14C0BBA71A3E0DFD61FEE4" box="[568,751,296,314]" gridcol="3" gridrow="1" pageId="2" pageNumber="128">47.4</td>
|
||
<td id="76E15DA4DF14C0BBA6303E0DFCE2FEE4" box="[786,876,296,314]" gridcol="4" gridrow="1" pageId="2" pageNumber="128">49.7/+2.3</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3E0DFBC2FEE4" box="[910,1100,296,314]" gridcol="5" gridrow="1" pageId="2" pageNumber="128">46.9</td>
|
||
<td id="76E15DA4DF14C0BBA14C3E0DFB72FEE4" box="[1134,1276,296,314]" gridcol="6" gridrow="1" pageId="2" pageNumber="128">49.4/+2.5</td>
|
||
<td id="76E15DA4DF14C0BBA03C3E0DFA22FEE4" box="[1310,1452,296,314]" gridcol="7" gridrow="1" pageId="2" pageNumber="128">49.7/+2.8</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3E66FA22FE8F" box="[110,1452,323,337]" gridrow="2" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1" rowspan-5="1">
|
||
<td id="76E15DA4DF14C0BBA14C3E66FB72FE8F" box="[1134,1276,323,337]" gridcol="6" gridrow="2" pageId="2" pageNumber="128">49.0/+2.1</td>
|
||
<td id="76E15DA4DF14C0BBA03C3E66FA22FE8F" box="[1310,1452,323,337]" gridcol="7" gridrow="2" pageId="2" pageNumber="128">49.6/+2.7</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3E73FA22FEB6" box="[110,1452,342,360]" gridrow="3" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3E73FF29FEB6" box="[110,167,342,360]" gridcol="0" gridrow="3" pageId="2" pageNumber="128">2</th>
|
||
<td id="76E15DA4DF14C0BBA5E83E73FEB5FEB6" box="[202,315,342,360]" gridcol="1" gridrow="3" pageId="2" pageNumber="128">48.6 g</td>
|
||
<td id="76E15DA4DF14C0BBA47C3E73FD9BFEB6" box="[350,533,342,360]" gridcol="2" gridrow="3" pageId="2" pageNumber="128">52.7</td>
|
||
<td id="76E15DA4DF14C0BBA71A3E73FD61FEB6" box="[568,751,342,360]" gridcol="3" gridrow="3" pageId="2" pageNumber="128">42.6</td>
|
||
<td id="76E15DA4DF14C0BBA6303E73FCE2FEB6" box="[786,876,342,360]" gridcol="4" gridrow="3" pageId="2" pageNumber="128">47.3/+4.7</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3E73FBC2FEB6" box="[910,1100,342,360]" gridcol="5" gridrow="3" pageId="2" pageNumber="128">43.5</td>
|
||
<td id="76E15DA4DF14C0BBA14C3E73FB72FEB6" box="[1134,1276,342,360]" gridcol="6" gridrow="3" pageId="2" pageNumber="128">47.9/+4.5</td>
|
||
<td id="76E15DA4DF14C0BBA03C3E73FA22FEB6" box="[1310,1452,342,360]" gridcol="7" gridrow="3" pageId="2" pageNumber="128">50.2/+6.8</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3E54FA22FEA1" box="[110,1452,369,383]" gridrow="4" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1">
|
||
<td id="76E15DA4DF14C0BBA6AC3E54FBC2FEA1" box="[910,1100,369,383]" gridcol="5" gridrow="4" pageId="2" pageNumber="128">43.3</td>
|
||
<td id="76E15DA4DF14C0BBA14C3E54FB72FEA1" box="[1134,1276,369,383]" gridcol="6" gridrow="4" pageId="2" pageNumber="128">48.0/+4.6</td>
|
||
<td id="76E15DA4DF14C0BBA03C3E54FA22FEA1" box="[1310,1452,369,383]" gridcol="7" gridrow="4" pageId="2" pageNumber="128">50.2/+6.8</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3EADFA22FE48" box="[110,1452,392,406]" gridrow="5" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3EADFF29FE48" box="[110,167,392,406]" gridcol="0" gridrow="5" pageId="2" pageNumber="128">3</th>
|
||
<td id="76E15DA4DF14C0BBA5E83EADFEB5FE48" box="[202,315,392,406]" gridcol="1" gridrow="5" pageId="2" pageNumber="128">147.3</td>
|
||
<td id="76E15DA4DF14C0BBA47C3EADFD9BFE48" box="[350,533,392,406]" gridcol="2" gridrow="5" pageId="2" pageNumber="128">36.3</td>
|
||
<td id="76E15DA4DF14C0BBA71A3EADFD61FE48" box="[568,751,392,406]" gridcol="3" gridrow="5" pageId="2" pageNumber="128">39.8</td>
|
||
<td id="76E15DA4DF14C0BBA6303EADFCE2FE48" box="[786,876,392,406]" gridcol="4" gridrow="5" pageId="2" pageNumber="128">45.4/+5.6</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3EADFBC2FE48" box="[910,1100,392,406]" gridcol="5" gridrow="5" pageId="2" pageNumber="128">48.1</td>
|
||
<td id="76E15DA4DF14C0BBA14C3EADFB72FE48" box="[1134,1276,392,406]" gridcol="6" gridrow="5" pageId="2" pageNumber="128">49.4/+2.4</td>
|
||
<td id="76E15DA4DF14C0BBA03C3EADFA22FE48" box="[1310,1452,392,406]" gridcol="7" gridrow="5" pageId="2" pageNumber="128">59.2/+12.2</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3EBBFA22FE72" box="[110,1452,414,428]" gridrow="6" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1">
|
||
<td id="76E15DA4DF14C0BBA6AC3EBBFBC2FE72" box="[910,1100,414,428]" gridcol="5" gridrow="6" pageId="2" pageNumber="128">45.8</td>
|
||
<td id="76E15DA4DF14C0BBA14C3EBBFB72FE72" box="[1134,1276,414,428]" gridcol="6" gridrow="6" pageId="2" pageNumber="128">51.6/+4.6</td>
|
||
<td id="76E15DA4DF14C0BBA03C3EBBFA22FE72" box="[1310,1452,414,428]" gridcol="7" gridrow="6" pageId="2" pageNumber="128">59.2/+12.2</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3E90FA22FE1A" box="[110,1452,437,452]" gridrow="7" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3E90FF29FE1A" box="[110,167,437,452]" gridcol="0" gridrow="7" pageId="2" pageNumber="128">4</th>
|
||
<td id="76E15DA4DF14C0BBA5E83E90FEB5FE1A" box="[202,315,437,452]" gridcol="1" gridrow="7" pageId="2" pageNumber="128">112.7</td>
|
||
<td id="76E15DA4DF14C0BBA47C3E90FD9BFE1A" box="[350,533,437,452]" gridcol="2" gridrow="7" pageId="2" pageNumber="128">148.9</td>
|
||
<td id="76E15DA4DF14C0BBA71A3E90FD61FE1A" box="[568,751,437,452]" gridcol="3" gridrow="7" pageId="2" pageNumber="128">71.2</td>
|
||
<td id="76E15DA4DF14C0BBA6303E90FCE2FE1A" box="[786,876,437,452]" gridcol="4" gridrow="7" pageId="2" pageNumber="128">75.7/+4.5</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3E90FBC2FE1A" box="[910,1100,437,452]" gridcol="5" gridrow="7" pageId="2" pageNumber="128">198.3</td>
|
||
<td id="76E15DA4DF14C0BBA14C3E90FB72FE1A" box="[1134,1276,437,452]" gridcol="6" gridrow="7" pageId="2" pageNumber="128">200.8/+2.6</td>
|
||
<td id="76E15DA4DF14C0BBA03C3E90FA22FE1A" box="[1310,1452,437,452]" gridcol="7" gridrow="7" pageId="2" pageNumber="128">
|
||
197.6/
|
||
<emphasis id="B974EA88DF143F46A0733E93FAD0FE1A" box="[1361,1374,438,452]" italics="true" pageId="2" pageNumber="128">—</emphasis>
|
||
0.6
|
||
</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3EE9FA22FE04" box="[110,1452,460,474]" gridrow="8" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1">
|
||
<td id="76E15DA4DF14C0BBA6AC3EE9FBC2FE04" box="[910,1100,460,474]" gridcol="5" gridrow="8" pageId="2" pageNumber="128">198.1</td>
|
||
<td id="76E15DA4DF14C0BBA14C3EE9FB72FE04" box="[1134,1276,460,474]" gridcol="6" gridrow="8" pageId="2" pageNumber="128">200.1/+1.9</td>
|
||
<td id="76E15DA4DF14C0BBA03C3EE9FA22FE04" box="[1310,1452,460,474]" gridcol="7" gridrow="8" pageId="2" pageNumber="128">198.4/+0.2</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3EFAFA22FE2F" box="[110,1452,479,497]" gridrow="9" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3EFAFF29FE2F" box="[110,167,479,497]" gridcol="0" gridrow="9" pageId="2" pageNumber="128">5</th>
|
||
<td id="76E15DA4DF14C0BBA5E83EFAFEB5FE2F" box="[202,315,479,497]" gridcol="1" gridrow="9" pageId="2" pageNumber="128">173.8</td>
|
||
<td id="76E15DA4DF14C0BBA47C3EFAFD9BFE2F" box="[350,533,479,497]" gridcol="2" gridrow="9" pageId="2" pageNumber="128">171.6</td>
|
||
<td id="76E15DA4DF14C0BBA71A3EFAFD61FE2F" box="[568,751,479,497]" gridcol="3" gridrow="9" pageId="2" pageNumber="128">72.2</td>
|
||
<td id="76E15DA4DF14C0BBA6303EFAFCE2FE2F" box="[786,876,479,497]" gridcol="4" gridrow="9" pageId="2" pageNumber="128">74.2/+2.0</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3EFAFBC2FE2F" box="[910,1100,479,497]" gridcol="5" gridrow="9" pageId="2" pageNumber="128">97.1</td>
|
||
<td id="76E15DA4DF14C0BBA14C3EFAFB72FE2F" box="[1134,1276,479,497]" gridcol="6" gridrow="9" pageId="2" pageNumber="128">99.5/+2.4</td>
|
||
<td id="76E15DA4DF14C0BBA03C3EFAFA22FE2F" box="[1310,1452,479,497]" gridcol="7" gridrow="9" pageId="2" pageNumber="128">98.0b/+0.9</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3ED3FA22FDD6" box="[110,1452,502,520]" gridrow="10" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1">
|
||
<td id="76E15DA4DF14C0BBA6AC3ED3FBC2FDD6" box="[910,1100,502,520]" gridcol="5" gridrow="10" pageId="2" pageNumber="128">97.0</td>
|
||
<td id="76E15DA4DF14C0BBA14C3ED3FB72FDD6" box="[1134,1276,502,520]" gridcol="6" gridrow="10" pageId="2" pageNumber="128">100.1/+3.0</td>
|
||
<td id="76E15DA4DF14C0BBA03C3ED3FA22FDD6" box="[1310,1452,502,520]" gridcol="7" gridrow="10" pageId="2" pageNumber="128">98.9b/+1.8</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3D28FA22FDC1" box="[110,1452,525,543]" gridrow="11" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3D28FF29FDC1" box="[110,167,525,543]" gridcol="0" gridrow="11" pageId="2" pageNumber="128">6</th>
|
||
<td id="76E15DA4DF14C0BBA5E83D28FEB5FDC1" box="[202,315,525,543]" gridcol="1" gridrow="11" pageId="2" pageNumber="128">120.7</td>
|
||
<td id="76E15DA4DF14C0BBA47C3D28FD9BFDC1" box="[350,533,525,543]" gridcol="2" gridrow="11" pageId="2" pageNumber="128">123.8</td>
|
||
<td id="76E15DA4DF14C0BBA71A3D28FD61FDC1" box="[568,751,525,543]" gridcol="3" gridrow="11" pageId="2" pageNumber="128">155.4</td>
|
||
<td id="76E15DA4DF14C0BBA6303D28FCE2FDC1" box="[786,876,525,543]" gridcol="4" gridrow="11" pageId="2" pageNumber="128">156.0/+0.6</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3D28FBC2FDC1" box="[910,1100,525,543]" gridcol="5" gridrow="11" pageId="2" pageNumber="128">144.5</td>
|
||
<td id="76E15DA4DF14C0BBA14C3D28FB72FDC1" box="[1134,1276,525,543]" gridcol="6" gridrow="11" pageId="2" pageNumber="128">
|
||
143.3/
|
||
<emphasis id="B974EA88DF143F46A1833D34FB20FDC1" box="[1185,1198,529,543]" italics="true" pageId="2" pageNumber="128">—</emphasis>
|
||
1.1
|
||
</td>
|
||
<td id="76E15DA4DF14C0BBA03C3D28FA22FDC1" box="[1310,1452,525,543]" gridcol="7" gridrow="11" pageId="2" pageNumber="128">163.7 c /+19.2</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3D01FA22FDE8" box="[110,1452,548,566]" gridrow="12" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1">
|
||
<td id="76E15DA4DF14C0BBA6AC3D01FBC2FDE8" box="[910,1100,548,566]" gridcol="5" gridrow="12" pageId="2" pageNumber="128">144.4</td>
|
||
<td id="76E15DA4DF14C0BBA14C3D01FB72FDE8" box="[1134,1276,548,566]" gridcol="6" gridrow="12" pageId="2" pageNumber="128">
|
||
144.0/
|
||
<emphasis id="B974EA88DF143F46A1833D0DFB20FDE8" box="[1185,1198,552,566]" italics="true" pageId="2" pageNumber="128">—</emphasis>
|
||
0.4
|
||
</td>
|
||
<td id="76E15DA4DF14C0BBA03C3D01FA22FDE8" box="[1310,1452,548,566]" gridcol="7" gridrow="12" pageId="2" pageNumber="128">163.8 c /+19.3</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3D1EFA22FD93" box="[110,1452,571,589]" gridrow="13" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3D1EFF29FD93" box="[110,167,571,589]" gridcol="0" gridrow="13" pageId="2" pageNumber="128">7</th>
|
||
<td id="76E15DA4DF14C0BBA5E83D1EFEB5FD93" box="[202,315,571,589]" gridcol="1" gridrow="13" pageId="2" pageNumber="128">160.7</td>
|
||
<td id="76E15DA4DF14C0BBA47C3D1EFD9BFD93" box="[350,533,571,589]" gridcol="2" gridrow="13" pageId="2" pageNumber="128">130.1</td>
|
||
<td id="76E15DA4DF14C0BBA71A3D1EFD61FD93" box="[568,751,571,589]" gridcol="3" gridrow="13" pageId="2" pageNumber="128">124.4</td>
|
||
<td id="76E15DA4DF14C0BBA6303D1EFCE2FD93" box="[786,876,571,589]" gridcol="4" gridrow="13" pageId="2" pageNumber="128">125.4/+1.0</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3D1EFBC2FD93" box="[910,1100,571,589]" gridcol="5" gridrow="13" pageId="2" pageNumber="128">135.2</td>
|
||
<td id="76E15DA4DF14C0BBA14C3D1EFB72FD93" box="[1134,1276,571,589]" gridcol="6" gridrow="13" pageId="2" pageNumber="128">
|
||
135.1/
|
||
<emphasis id="B974EA88DF143F46A1833D1AFB20FD93" box="[1185,1198,575,589]" italics="true" pageId="2" pageNumber="128">—</emphasis>
|
||
0.05
|
||
</td>
|
||
<td id="76E15DA4DF14C0BBA03C3D1EFA22FD93" box="[1310,1452,571,589]" gridcol="7" gridrow="13" pageId="2" pageNumber="128">
|
||
123.9d/
|
||
<emphasis id="B974EA88DF143F46A07B3D1AFAE8FD93" box="[1369,1382,575,589]" italics="true" pageId="2" pageNumber="128">—</emphasis>
|
||
11.3
|
||
</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3D74FA22FDBA" box="[110,1452,593,612]" gridrow="14" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1">
|
||
<td id="76E15DA4DF14C0BBA6AC3D74FBC2FDBA" box="[910,1100,593,612]" gridcol="5" gridrow="14" pageId="2" pageNumber="128">135.1</td>
|
||
<td id="76E15DA4DF14C0BBA14C3D74FB72FDBA" box="[1134,1276,593,612]" gridcol="6" gridrow="14" pageId="2" pageNumber="128">136.0/+0.8</td>
|
||
<td id="76E15DA4DF14C0BBA03C3D74FA22FDBA" box="[1310,1452,593,612]" gridcol="7" gridrow="14" pageId="2" pageNumber="128">
|
||
123.1d/
|
||
<emphasis id="B974EA88DF143F46A07B3D73FAE8FDBA" box="[1369,1382,598,612]" italics="true" pageId="2" pageNumber="128">—</emphasis>
|
||
12.1
|
||
</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3D49FA22FDA5" box="[110,1452,620,635]" gridrow="15" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3D49FF29FDA5" box="[110,167,620,635]" gridcol="0" gridrow="15" pageId="2" pageNumber="128">8</th>
|
||
<td id="76E15DA4DF14C0BBA5E83D49FEB5FDA5" box="[202,315,620,635]" gridcol="1" gridrow="15" pageId="2" pageNumber="128">68.8</td>
|
||
<td id="76E15DA4DF14C0BBA47C3D49FD9BFDA5" box="[350,533,620,635]" gridcol="2" gridrow="15" pageId="2" pageNumber="128">131.5</td>
|
||
<td id="76E15DA4DF14C0BBA71A3D49FD61FDA5" box="[568,751,620,635]" gridcol="3" gridrow="15" pageId="2" pageNumber="128">110.5</td>
|
||
<td id="76E15DA4DF14C0BBA6303D49FCE2FDA5" box="[786,876,620,635]" gridcol="4" gridrow="15" pageId="2" pageNumber="128">
|
||
109.2/
|
||
<emphasis id="B974EA88DF143F46A6673D48FCDCFDA5" box="[837,850,621,635]" italics="true" pageId="2" pageNumber="128">—</emphasis>
|
||
1.3
|
||
</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3D49FBC2FDA5" box="[910,1100,620,635]" gridcol="5" gridrow="15" pageId="2" pageNumber="128">112.8</td>
|
||
<td id="76E15DA4DF14C0BBA14C3D49FB72FDA5" box="[1134,1276,620,635]" gridcol="6" gridrow="15" pageId="2" pageNumber="128">
|
||
111.4/
|
||
<emphasis id="B974EA88DF143F46A1833D48FB20FDA5" box="[1185,1198,621,635]" italics="true" pageId="2" pageNumber="128">—</emphasis>
|
||
1.1
|
||
</td>
|
||
<td id="76E15DA4DF14C0BBA03C3D49FA22FDA5" box="[1310,1452,620,635]" gridcol="7" gridrow="15" pageId="2" pageNumber="128">113.7/+1.1</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3DA6FA22FD4C" box="[110,1452,643,658]" gridrow="16" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1">
|
||
<td id="76E15DA4DF14C0BBA6AC3DA6FBC2FD4C" box="[910,1100,643,658]" gridcol="5" gridrow="16" pageId="2" pageNumber="128">112.3</td>
|
||
<td id="76E15DA4DF14C0BBA14C3DA6FB72FD4C" box="[1134,1276,643,658]" gridcol="6" gridrow="16" pageId="2" pageNumber="128">
|
||
111.8/
|
||
<emphasis id="B974EA88DF143F46A1833DA1FB20FD4C" box="[1185,1198,644,658]" italics="true" pageId="2" pageNumber="128">—</emphasis>
|
||
0.7
|
||
</td>
|
||
<td id="76E15DA4DF14C0BBA03C3DA6FA22FD4C" box="[1310,1452,643,658]" gridcol="7" gridrow="16" pageId="2" pageNumber="128">114.0/+1.4</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3DB3FA22FD76" box="[110,1452,662,680]" gridrow="17" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3DB3FF29FD76" box="[110,167,662,680]" gridcol="0" gridrow="17" pageId="2" pageNumber="128">9</th>
|
||
<td id="76E15DA4DF14C0BBA5E83DB3FEB5FD76" box="[202,315,662,680]" gridcol="1" gridrow="17" pageId="2" pageNumber="128">47.2 g</td>
|
||
<td id="76E15DA4DF14C0BBA47C3DB3FD9BFD76" box="[350,533,662,680]" gridcol="2" gridrow="17" pageId="2" pageNumber="128">83.3</td>
|
||
<td id="76E15DA4DF14C0BBA71A3DB3FD61FD76" box="[568,751,662,680]" gridcol="3" gridrow="17" pageId="2" pageNumber="128">160.4</td>
|
||
<td id="76E15DA4DF14C0BBA6303DB3FCE2FD76" box="[786,876,662,680]" gridcol="4" gridrow="17" pageId="2" pageNumber="128">165.2/+5.2</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3DB3FBC2FD76" box="[910,1100,662,680]" gridcol="5" gridrow="17" pageId="2" pageNumber="128">171.1</td>
|
||
<td id="76E15DA4DF14C0BBA14C3DB3FB72FD76" box="[1134,1276,662,680]" gridcol="6" gridrow="17" pageId="2" pageNumber="128">178.8/+7.8</td>
|
||
<td id="76E15DA4DF14C0BBA03C3DB3FA22FD76" box="[1310,1452,662,680]" gridcol="7" gridrow="17" pageId="2" pageNumber="128">181.9/+10.9</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3D94FA22FD61" box="[110,1452,689,703]" gridrow="18" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1">
|
||
<td id="76E15DA4DF14C0BBA6AC3D94FBC2FD61" box="[910,1100,689,703]" gridcol="5" gridrow="18" pageId="2" pageNumber="128">170.9</td>
|
||
<td id="76E15DA4DF14C0BBA14C3D94FB72FD61" box="[1134,1276,689,703]" gridcol="6" gridrow="18" pageId="2" pageNumber="128">181.3/+10.3</td>
|
||
<td id="76E15DA4DF14C0BBA03C3D94FA22FD61" box="[1310,1452,689,703]" gridcol="7" gridrow="18" pageId="2" pageNumber="128">182.9/+11.9</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3DE1FA22FD08" box="[110,1452,708,726]" gridrow="19" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3DE1FF29FD08" box="[110,167,708,726]" gridcol="0" gridrow="19" pageId="2" pageNumber="128">10</th>
|
||
<td id="76E15DA4DF14C0BBA5E83DE1FEB5FD08" box="[202,315,708,726]" gridcol="1" gridrow="19" pageId="2" pageNumber="128">43.7f</td>
|
||
<td id="76E15DA4DF14C0BBA47C3DE1FD9BFD08" box="[350,533,708,726]" gridcol="2" gridrow="19" pageId="2" pageNumber="128">58.0</td>
|
||
<td id="76E15DA4DF14C0BBA71A3DE1FD61FD08" box="[568,751,708,726]" gridcol="3" gridrow="19" pageId="2" pageNumber="128">50.1</td>
|
||
<td id="76E15DA4DF14C0BBA6303DE1FCE2FD08" box="[786,876,708,726]" gridcol="4" gridrow="19" pageId="2" pageNumber="128">52.8/+2.7</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3DE1FBC2FD08" box="[910,1100,708,726]" gridcol="5" gridrow="19" pageId="2" pageNumber="128">50.9</td>
|
||
<td id="76E15DA4DF14C0BBA14C3DE1FB72FD08" box="[1134,1276,708,726]" gridcol="6" gridrow="19" pageId="2" pageNumber="128">54.5/+3.6</td>
|
||
<td id="76E15DA4DF14C0BBA03C3DE1FA22FD08" box="[1310,1452,708,726]" gridcol="7" gridrow="19" pageId="2" pageNumber="128">54.7/+3.8</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3DFBFA22FD32" box="[110,1452,734,748]" gridrow="20" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1">
|
||
<td id="76E15DA4DF14C0BBA6AC3DFBFBC2FD32" box="[910,1100,734,748]" gridcol="5" gridrow="20" pageId="2" pageNumber="128">50.8</td>
|
||
<td id="76E15DA4DF14C0BBA14C3DFBFB72FD32" box="[1134,1276,734,748]" gridcol="6" gridrow="20" pageId="2" pageNumber="128">54.6/+3.7</td>
|
||
<td id="76E15DA4DF14C0BBA03C3DFBFA22FD32" box="[1310,1452,734,748]" gridcol="7" gridrow="20" pageId="2" pageNumber="128">54.7/+3.8</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3DD0FA22FCDD" box="[110,1452,757,771]" gridrow="21" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3DD0FF29FCDD" box="[110,167,757,771]" gridcol="0" gridrow="21" pageId="2" pageNumber="128">11</th>
|
||
<td id="76E15DA4DF14C0BBA5E83DD0FEB5FCDD" box="[202,315,757,771]" gridcol="1" gridrow="21" pageId="2" pageNumber="128">34.4</td>
|
||
<td id="76E15DA4DF14C0BBA47C3DD0FD9BFCDD" box="[350,533,757,771]" gridcol="2" gridrow="21" pageId="2" pageNumber="128">33.2</td>
|
||
<td id="76E15DA4DF14C0BBA71A3DD0FD61FCDD" box="[568,751,757,771]" gridcol="3" gridrow="21" pageId="2" pageNumber="128">37.8</td>
|
||
<td id="76E15DA4DF14C0BBA6303DD0FCE2FCDD" box="[786,876,757,771]" gridcol="4" gridrow="21" pageId="2" pageNumber="128">44.0/+6.2</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3DD0FBC2FCDD" box="[910,1100,757,771]" gridcol="5" gridrow="21" pageId="2" pageNumber="128">37.4</td>
|
||
<td id="76E15DA4DF14C0BBA14C3DD0FB72FCDD" box="[1134,1276,757,771]" gridcol="6" gridrow="21" pageId="2" pageNumber="128">42.4/+5.0</td>
|
||
<td id="76E15DA4DF14C0BBA03C3DD0FA22FCDD" box="[1310,1452,757,771]" gridcol="7" gridrow="21" pageId="2" pageNumber="128">44.0/+6.7</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3C29FA22FCC4" box="[110,1452,780,794]" gridrow="22" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1">
|
||
<td id="76E15DA4DF14C0BBA6AC3C29FBC2FCC4" box="[910,1100,780,794]" gridcol="5" gridrow="22" pageId="2" pageNumber="128">37.1</td>
|
||
<td id="76E15DA4DF14C0BBA14C3C29FB72FCC4" box="[1134,1276,780,794]" gridcol="6" gridrow="22" pageId="2" pageNumber="128">42.8/+5.4</td>
|
||
<td id="76E15DA4DF14C0BBA03C3C29FA22FCC4" box="[1310,1452,780,794]" gridcol="7" gridrow="22" pageId="2" pageNumber="128">43.9/+6.6</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3C06FA22FCEF" box="[110,1452,803,817]" gridrow="23" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3C06FF29FCEF" box="[110,167,803,817]" gridcol="0" gridrow="23" pageId="2" pageNumber="128">12</th>
|
||
<td id="76E15DA4DF14C0BBA5E83C06FEB5FCEF" box="[202,315,803,817]" gridcol="1" gridrow="23" pageId="2" pageNumber="128">26.2</td>
|
||
<td id="76E15DA4DF14C0BBA47C3C06FD9BFCEF" box="[350,533,803,817]" gridcol="2" gridrow="23" pageId="2" pageNumber="128">17.7</td>
|
||
<td id="76E15DA4DF14C0BBA71A3C06FD61FCEF" box="[568,751,803,817]" gridcol="3" gridrow="23" pageId="2" pageNumber="128">15.6</td>
|
||
<td id="76E15DA4DF14C0BBA6303C06FCE2FCEF" box="[786,876,803,817]" gridcol="4" gridrow="23" pageId="2" pageNumber="128">16.6/+1.0</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3C06FBC2FCEF" box="[910,1100,803,817]" gridcol="5" gridrow="23" pageId="2" pageNumber="128">13.0</td>
|
||
<td id="76E15DA4DF14C0BBA14C3C06FB72FCEF" box="[1134,1276,803,817]" gridcol="6" gridrow="23" pageId="2" pageNumber="128">14.5/+1.9</td>
|
||
<td id="76E15DA4DF14C0BBA03C3C06FA22FCEF" box="[1310,1452,803,817]" gridcol="7" gridrow="23" pageId="2" pageNumber="128">19.8/+7.2</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3C1FFA22FC96" box="[110,1452,826,840]" gridrow="24" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1">
|
||
<td id="76E15DA4DF14C0BBA6AC3C1FFBC2FC96" box="[910,1100,826,840]" gridcol="5" gridrow="24" pageId="2" pageNumber="128">12.2</td>
|
||
<td id="76E15DA4DF14C0BBA14C3C1FFB72FC96" box="[1134,1276,826,840]" gridcol="6" gridrow="24" pageId="2" pageNumber="128">15.0/+2.4</td>
|
||
<td id="76E15DA4DF14C0BBA03C3C1FFA22FC96" box="[1310,1452,826,840]" gridcol="7" gridrow="24" pageId="2" pageNumber="128">19.7/+7.1</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3C68FA22FC81" box="[110,1452,845,863]" gridrow="25" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3C68FF29FC81" box="[110,167,845,863]" gridcol="0" gridrow="25" pageId="2" pageNumber="128">13</th>
|
||
<td id="76E15DA4DF14C0BBA5E83C68FEB5FC81" box="[202,315,845,863]" gridcol="1" gridrow="25" pageId="2" pageNumber="128">70.0</td>
|
||
<td id="76E15DA4DF14C0BBA47C3C68FD9BFC81" box="[350,533,845,863]" gridcol="2" gridrow="25" pageId="2" pageNumber="128">69.8</td>
|
||
<td id="76E15DA4DF14C0BBA71A3C68FD61FC81" box="[568,751,845,863]" gridcol="3" gridrow="25" pageId="2" pageNumber="128">174,8</td>
|
||
<td id="76E15DA4DF14C0BBA6303C68FCE2FC81" box="[786,876,845,863]" gridcol="4" gridrow="25" pageId="2" pageNumber="128">
|
||
172.4/
|
||
<emphasis id="B974EA88DF143F46A6673C74FCDCFC81" box="[837,850,849,863]" italics="true" pageId="2" pageNumber="128">—</emphasis>
|
||
2.4
|
||
</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3C68FBC2FC81" box="[910,1100,845,863]" gridcol="5" gridrow="25" pageId="2" pageNumber="128">169.7</td>
|
||
<td id="76E15DA4DF14C0BBA14C3C68FB72FC81" box="[1134,1276,845,863]" gridcol="6" gridrow="25" pageId="2" pageNumber="128">169.9/+0.2</td>
|
||
<td id="76E15DA4DF14C0BBA03C3C68FA22FC81" box="[1310,1452,845,863]" gridcol="7" gridrow="25" pageId="2" pageNumber="128">
|
||
165.1 e /
|
||
<emphasis id="B974EA88DF143F46A07A3C74FAEBFC81" box="[1368,1381,849,863]" italics="true" pageId="2" pageNumber="128">—</emphasis>
|
||
4.6
|
||
</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3C41FA22FCA8" box="[110,1452,868,886]" gridrow="26" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1" rowspan-5="1">
|
||
<td id="76E15DA4DF14C0BBA14C3C41FB72FCA8" box="[1134,1276,868,886]" gridcol="6" gridrow="26" pageId="2" pageNumber="128">170.2/+0.5</td>
|
||
<td id="76E15DA4DF14C0BBA03C3C41FA22FCA8" box="[1310,1452,868,886]" gridcol="7" gridrow="26" pageId="2" pageNumber="128">
|
||
166.7e /
|
||
<emphasis id="B974EA88DF143F46A07A3C4DFAEBFCA8" box="[1368,1381,872,886]" italics="true" pageId="2" pageNumber="128">—</emphasis>
|
||
3.0
|
||
</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3C5FFA22FC52" box="[110,1452,890,908]" gridrow="27" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3C5FFF29FC52" box="[110,167,890,908]" gridcol="0" gridrow="27" pageId="2" pageNumber="128">14</th>
|
||
<td id="76E15DA4DF14C0BBA5E83C5FFEB5FC52" box="[202,315,890,908]" gridcol="1" gridrow="27" pageId="2" pageNumber="128">32.2h</td>
|
||
<td id="76E15DA4DF14C0BBA47C3C5FFD9BFC52" box="[350,533,890,908]" gridcol="2" gridrow="27" pageId="2" pageNumber="128">32.6f</td>
|
||
<td id="76E15DA4DF14C0BBA71A3C5FFD61FC52" box="[568,751,890,908]" gridcol="3" gridrow="27" pageId="2" pageNumber="128">29.2</td>
|
||
<td id="76E15DA4DF14C0BBA6303C5FFCE2FC52" box="[786,876,890,908]" gridcol="4" gridrow="27" pageId="2" pageNumber="128">30.8/+1.6</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3C5FFBC2FC52" box="[910,1100,890,908]" gridcol="5" gridrow="27" pageId="2" pageNumber="128">29.0</td>
|
||
<td id="76E15DA4DF14C0BBA14C3C5FFB72FC52" box="[1134,1276,890,908]" gridcol="6" gridrow="27" pageId="2" pageNumber="128">31.4/+2.4</td>
|
||
<td id="76E15DA4DF14C0BBA03C3C5FFA22FC52" box="[1310,1452,890,908]" gridcol="7" gridrow="27" pageId="2" pageNumber="128">30.1/+1.1</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3CB0FA22FC7D" box="[110,1452,917,931]" gridrow="28" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1">
|
||
<td id="76E15DA4DF14C0BBA6AC3CB0FBC2FC7D" box="[910,1100,917,931]" gridcol="5" gridrow="28" pageId="2" pageNumber="128">28.9</td>
|
||
<td id="76E15DA4DF14C0BBA14C3CB0FB72FC7D" box="[1134,1276,917,931]" gridcol="6" gridrow="28" pageId="2" pageNumber="128">30.1/+1.1</td>
|
||
<td id="76E15DA4DF14C0BBA03C3CB0FA22FC7D" box="[1310,1452,917,931]" gridcol="7" gridrow="28" pageId="2" pageNumber="128">30.1/+1.1</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3C8DFA22FC64" box="[110,1452,936,954]" gridrow="29" pageId="2" pageNumber="128">
|
||
<th id="76E15DA4DF14C0BBA54C3C8DFF29FC64" box="[110,167,936,954]" gridcol="0" gridrow="29" pageId="2" pageNumber="128">15</th>
|
||
<td id="76E15DA4DF14C0BBA5E83C8DFEB5FC64" box="[202,315,936,954]" gridcol="1" gridrow="29" pageId="2" pageNumber="128">31.0h</td>
|
||
<td id="76E15DA4DF14C0BBA47C3C8DFD9BFC64" box="[350,533,936,954]" gridcol="2" gridrow="29" pageId="2" pageNumber="128">32.9f</td>
|
||
<td id="76E15DA4DF14C0BBA71A3C8DFD61FC64" box="[568,751,936,954]" gridcol="3" gridrow="29" pageId="2" pageNumber="128">26.8</td>
|
||
<td id="76E15DA4DF14C0BBA6303C8DFCE2FC64" box="[786,876,936,954]" gridcol="4" gridrow="29" pageId="2" pageNumber="128">28.0/+1.2</td>
|
||
<td id="76E15DA4DF14C0BBA6AC3C8DFBC2FC64" box="[910,1100,936,954]" gridcol="5" gridrow="29" pageId="2" pageNumber="128">26.4</td>
|
||
<td id="76E15DA4DF14C0BBA14C3C8DFB72FC64" box="[1134,1276,936,954]" gridcol="6" gridrow="29" pageId="2" pageNumber="128">27.7/+1.3</td>
|
||
<td id="76E15DA4DF14C0BBA03C3C8DFA22FC64" box="[1310,1452,936,954]" gridcol="7" gridrow="29" pageId="2" pageNumber="128">27.9/+1.5</td>
|
||
</tr>
|
||
<tr id="353034D8DF14C0BBA54C3CE6FA22FC0F" box="[110,1452,963,977]" gridrow="30" pageId="2" pageNumber="128" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1">
|
||
<td id="76E15DA4DF14C0BBA6AC3CE6FBC2FC0F" box="[910,1100,963,977]" gridcol="5" gridrow="30" pageId="2" pageNumber="128">26.3</td>
|
||
<td id="76E15DA4DF14C0BBA14C3CE6FB72FC0F" box="[1134,1276,963,977]" gridcol="6" gridrow="30" pageId="2" pageNumber="128">27.6/+1.2</td>
|
||
<td id="76E15DA4DF14C0BBA03C3CE6FA22FC0F" box="[1310,1452,963,977]" gridcol="7" gridrow="30" pageId="2" pageNumber="128">27.8/+1.4</td>
|
||
</tr>
|
||
</table>
|
||
</paragraph>
|
||
<tableNote id="76E63714DF143F46A5453CC3FDF7FBB4" pageId="2" pageNumber="128" targetBox="[110,1452,263,977]" targetPageId="2">
|
||
<paragraph id="8BBF369ADF143F46A5453CC3FDBBFC26" blockId="2.[87,633,998,1131]" box="[103,565,998,1016]" pageId="2" pageNumber="128">
|
||
<superScript id="7C759BD2DF143F46A5453CC3FFE0FC31" attach="left" box="[103,110,998,1007]" fontSize="4" pageId="2" pageNumber="128">a</superScript>
|
||
The pairs of signals are due to a C-5 epimeric mixture.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF143F46A5443CD8FE75FBD1" blockId="2.[87,633,998,1131]" box="[102,507,1021,1039]" pageId="2" pageNumber="128">
|
||
<superScript id="7C759BD2DF143F46A5443CD8FFE3FBD9" attach="left" box="[102,109,1021,1031]" fontSize="4" pageId="2" pageNumber="128">b</superScript>
|
||
The calculated resonance refers to carbon C-13.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF143F46A5453B31FE7FFBF8" blockId="2.[87,633,998,1131]" box="[103,497,1044,1062]" pageId="2" pageNumber="128">
|
||
<superScript id="7C759BD2DF143F46A5453B31FFE3FBC3" attach="left" box="[103,109,1044,1053]" fontSize="4" pageId="2" pageNumber="128">c</superScript>
|
||
The calculated resonance refers to carbon C-7.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF143F46A5443B0FFE7FFBE2" blockId="2.[87,633,998,1131]" box="[102,497,1066,1085]" pageId="2" pageNumber="128">
|
||
<superScript id="7C759BD2DF143F46A5443B0FFFE0FBEA" attach="left" box="[102,110,1066,1076]" fontSize="4" pageId="2" pageNumber="128">d</superScript>
|
||
The calculated resonance refers to carbon C-6.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF143F46A5453B67FE7FFB8D" blockId="2.[87,633,998,1131]" box="[103,497,1090,1108]" pageId="2" pageNumber="128">
|
||
<superScript id="7C759BD2DF143F46A5453B67FFE0FB95" attach="left" box="[103,110,1090,1099]" fontSize="4" pageId="2" pageNumber="128">e</superScript>
|
||
The calculated resonance refers to carbon C-5.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF143F46A5753B7DFDF7FBB4" blockId="2.[87,633,998,1131]" box="[87,633,1112,1131]" pageId="2" pageNumber="128">
|
||
<superScript id="7C759BD2DF143F46A5753B7DFFFEFBBC" attach="left" box="[87,112,1112,1122]" fontSize="4" pageId="2" pageNumber="128">f,g,h</superScript>
|
||
Assignments in the same vertical column can be interchanged.
|
||
</paragraph>
|
||
</tableNote>
|
||
<paragraph id="8BBF369ADF143F46A6663BBDFA4CF993" blockId="2.[805,1474,1176,1614]" pageId="2" pageNumber="128">
|
||
The COSY spectrum of russulanobiline B
|
||
<emphasis id="B974EA88DF143F46A1FD3BBDFB76FB75" bold="true" box="[1247,1272,1176,1195]" pageId="2" pageNumber="128">13</emphasis>
|
||
showed four different proton spin systems, namely: (i) an isolated AB system (
|
||
<emphasis id="B974EA88DF143F46A60F3BEBFCBAFB3C" box="[813,820,1230,1250]" italics="true" pageId="2" pageNumber="128">J</emphasis>
|
||
<subScript id="178434DFDF143F46A6113BFCFCC9FB3B" attach="left" box="[819,839,1241,1253]" fontSize="5" pageId="2" pageNumber="128">AB</subScript>
|
||
= 17.4 Hz) centered at
|
||
<emphasis id="B974EA88DF143F46A1093BF5FBB8FB3D" box="[1067,1078,1232,1251]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A1143BFCFBCCFB3B" attach="left" box="[1078,1090,1241,1253]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
4.91, assigned to H
|
||
<subScript id="178434DFDF143F46A0223BFCFA87FB3B" attach="left" box="[1280,1289,1241,1253]" fontSize="5" pageId="2" pageNumber="128">2</subScript>
|
||
-5; (ii) a broad singlet at
|
||
<emphasis id="B974EA88DF143F46A6533BC9FCF2FB21" box="[881,892,1260,1279]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A65E3BD0FC06FADF" attach="left" box="[892,904,1269,1281]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
6.12, allylically coupled (
|
||
<emphasis id="B974EA88DF143F46A1B43BCFFB13FB20" box="[1174,1181,1258,1278]" italics="true" pageId="2" pageNumber="128">J</emphasis>
|
||
ca.1 Hz) to
|
||
<subScript id="178434DFDF143F46A03F3BC9FAB0FB21" attach="left" box="[1309,1342,1260,1281]" fontSize="5" pageId="2" pageNumber="128">Hβ-</subScript>
|
||
10 (
|
||
<emphasis id="B974EA88DF143F46A0483BC9FAFBFB21" box="[1386,1397,1260,1279]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A0563BD0FA0EFADF" attach="left" box="[1396,1408,1269,1281]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
2.45), attributed to H-8; (iii) an extended spin system encompassing from H-4 at
|
||
<emphasis id="B974EA88DF143F46A6493A06FCF8FAE8" box="[875,886,1315,1334]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A6543A09FC0CFAE6" attach="left" box="[886,898,1324,1336]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
4.34 to
|
||
<subScript id="178434DFDF143F46A6F73A01FC75FAE8" attach="left" box="[981,1019,1315,1337]" fontSize="7" pageId="2" pageNumber="128">Hoi-</subScript>
|
||
1 at
|
||
<emphasis id="B974EA88DF143F46A1053A06FBBCFAE8" box="[1063,1074,1315,1334]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A1103A09FBB0FAE6" attach="left" box="[1074,1086,1324,1336]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
1.77 and
|
||
<subScript id="178434DFDF143F46A1803A01FB4BFAE8" attach="left" box="[1186,1221,1315,1337]" fontSize="5" pageId="2" pageNumber="128">Hβ-</subScript>
|
||
1 at
|
||
<emphasis id="B974EA88DF143F46A1D33A06FB72FAE8" box="[1265,1276,1315,1334]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A1DE3A09FA86FAE6" attach="left" box="[1276,1288,1324,1336]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
1.51, through H-3 centered at
|
||
<emphasis id="B974EA88DF143F46A6BB3A1AFC2AFA8C" box="[921,932,1343,1362]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A6863A6DFC3EFA8A" attach="left" box="[932,944,1352,1364]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
1.86 and H-2 centered at
|
||
<emphasis id="B974EA88DF143F46A18D3A1AFB34FA8C" box="[1199,1210,1343,1362]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A1983A6DFB48FA8A" attach="left" box="[1210,1222,1352,1364]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
2.83, with H-3 being also coupled to Me-12 (
|
||
<emphasis id="B974EA88DF143F46A6C63A7FFC65FAB0" box="[996,1003,1370,1390]" italics="true" pageId="2" pageNumber="128">J</emphasis>
|
||
= 7.2 Hz); iv) a broad AB system (
|
||
<emphasis id="B974EA88DF143F46A01F3A7FFACAFAB0" box="[1341,1348,1370,1390]" italics="true" pageId="2" pageNumber="128">J</emphasis>
|
||
<subScript id="178434DFDF143F46A0613A41FAD9FAAE" attach="left" box="[1347,1367,1380,1392]" fontSize="5" pageId="2" pageNumber="128">AB</subScript>
|
||
= 17.3 Hz) centered at
|
||
<emphasis id="B974EA88DF143F46A6BB3A52FC2AFA54" box="[921,932,1399,1418]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A6863AA5FC3EFA52" attach="left" box="[932,944,1408,1420]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
2.40, assigned to H
|
||
<subScript id="178434DFDF143F46A14F3AA5FBF8FA52" attach="left" box="[1133,1142,1408,1420]" fontSize="5" pageId="2" pageNumber="128">2</subScript>
|
||
-10. The signal of
|
||
<subScript id="178434DFDF143F46A0063A52FACBFA54" attach="left" box="[1316,1349,1399,1420]" fontSize="5" pageId="2" pageNumber="128">Hβ-</subScript>
|
||
10 at
|
||
<emphasis id="B974EA88DF143F46A0593A52FA08FA54" box="[1403,1414,1399,1418]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A0A43AA5FA1CFA52" attach="left" box="[1414,1426,1408,1420]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
2.45 also showed two long range couplings (
|
||
<emphasis id="B974EA88DF143F46A1E03AB7FB47FA78" box="[1218,1225,1426,1446]" italics="true" pageId="2" pageNumber="128">J</emphasis>
|
||
ca.1 Hz) with H-8 at
|
||
<emphasis id="B974EA88DF143F46A0893AB6FA38FA78" box="[1451,1462,1427,1446]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A0943AB9FA4CFA76" attach="left" box="[1462,1474,1436,1448]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
6.12 and H-2 at
|
||
<emphasis id="B974EA88DF143F46A6F33A8AFC52FA1C" box="[977,988,1455,1474]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A6FE3A9DFC66FA1A" attach="left" box="[988,1000,1464,1476]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
2.83, while
|
||
<subScript id="178434DFDF143F46A1483A8AFB03FA1C" attach="left" box="[1130,1165,1455,1477]" fontSize="7" pageId="2" pageNumber="128">Hoi-</subScript>
|
||
10 at
|
||
<emphasis id="B974EA88DF143F46A1EE3A8AFB59FA1C" box="[1228,1239,1455,1474]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A1F53A9DFB6DFA1A" attach="left" box="[1239,1251,1464,1476]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
2.35 also exhibited a W-type coupling with
|
||
<subScript id="178434DFDF143F46A1253AEEFBA2FA00" attach="left" box="[1031,1068,1483,1504]" fontSize="7" pageId="2" pageNumber="128">Hoi-</subScript>
|
||
1 at
|
||
<emphasis id="B974EA88DF143F46A1753AEEFBECFA00" box="[1111,1122,1483,1502]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A1403AF1FBE0FA3E" attach="left" box="[1122,1134,1492,1504]" fontSize="5" pageId="2" pageNumber="128">H</subScript>
|
||
1.77. The
|
||
<superScript id="7C759BD2DF143F46A1F63AE2FB69FA0D" attach="right" box="[1236,1255,1479,1491]" fontSize="5" pageId="2" pageNumber="128">13</superScript>
|
||
C NMR spectrum confirmed the presence of an oxygenated methine (C-4) at
|
||
<emphasis id="B974EA88DF143F46A06F3AC2FAD6FA24" box="[1357,1368,1511,1530]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A07A3AD5FAECFA22" attach="left" box="[1368,1378,1520,1532]" fontSize="5" pageId="2" pageNumber="128">C</subScript>
|
||
71.2, and a Ƴ- lactone carbonyl group (C-13) at
|
||
<emphasis id="B974EA88DF143F46A1933926FB32F9C8" box="[1201,1212,1539,1558]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A19E392EFB48F9C9" attach="left" box="[1212,1222,1547,1559]" fontSize="5" pageId="2" pageNumber="128">C</subScript>
|
||
174.8, cross-conjugated with a 1,3-diene system formed by a tetrasubstituted olefin [
|
||
<emphasis id="B974EA88DF143F46A08F393AFA36F9EC" box="[1453,1464,1567,1586]" italics="true" pageId="2" pageNumber="128">δ</emphasis>
|
||
<subScript id="178434DFDF143F46A09A3902FA4CF9ED" attach="left" box="[1464,1474,1575,1587]" fontSize="5" pageId="2" pageNumber="128">C</subScript>
|
||
124.4 (s, C-7) and 155.4 (s, C-6)] and a trisubstituted double bond
|
||
</paragraph>
|
||
<caption id="DF7F6612DF143F46A49138EAFBE9F803" ID-DOI="http://doi.org/10.5281/zenodo.10491070" ID-Zenodo-Dep="10491070" box="[435,1127,1999,2013]" httpUri="https://zenodo.org/record/10491070/files/figure.png" pageId="2" pageNumber="128" startId="2.[435,461,1999,2013]" targetBox="[336,1294,1646,1967]" targetPageId="2" targetType="figure">
|
||
<paragraph id="8BBF369ADF143F46A49138EAFBE9F803" blockId="2.[435,1127,1999,2013]" box="[435,1127,1999,2013]" pageId="2" pageNumber="128">
|
||
<emphasis id="B974EA88DF143F46A49138EAFE6BF803" bold="true" box="[435,485,1999,2013]" pageId="2" pageNumber="128">Fig. 1.</emphasis>
|
||
Characteristic HMBC (a) and NOESY correlations (b) of russulanobiline A (
|
||
<emphasis id="B974EA88DF143F46A16538EAFBD5F803" bold="true" box="[1095,1115,1999,2013]" pageId="2" pageNumber="128">12</emphasis>
|
||
).
|
||
</paragraph>
|
||
</caption>
|
||
<caption id="DF7F6612DF153F47A5B63D5CFD60FD59" ID-DOI="http://doi.org/10.5281/zenodo.10491072" ID-Zenodo-Dep="10491072" box="[148,750,633,647]" httpUri="https://zenodo.org/record/10491072/files/figure.png" pageId="3" pageNumber="129" startId="3.[148,174,633,647]" targetBox="[147,751,183,601]" targetPageId="3" targetType="figure">
|
||
<paragraph id="8BBF369ADF153F47A5B63D5CFD60FD59" blockId="3.[148,750,633,647]" box="[148,750,633,647]" pageId="3" pageNumber="129">
|
||
<emphasis id="B974EA88DF153F47A5B63D5CFF48FD59" bold="true" box="[148,198,633,647]" pageId="3" pageNumber="129">Fig. 2.</emphasis>
|
||
Modeled minimum energy conformation of russulanobiline A (
|
||
<emphasis id="B974EA88DF153F47A7EC3D5CFD6CFD59" bold="true" box="[718,738,633,647]" pageId="3" pageNumber="129">12</emphasis>
|
||
).
|
||
</paragraph>
|
||
</caption>
|
||
<paragraph id="8BBF369ADF153F47A5533DEFFC9EFBD1" blockId="3.[113,784,712,1151]" pageId="3" pageNumber="129">
|
||
[
|
||
<emphasis id="B974EA88DF153F47A55B3DECFF0AFD02" box="[121,132,713,732]" italics="true" pageId="3" pageNumber="129">δ</emphasis>
|
||
<subScript id="178434DFDF153F47A5A63DF7FF00FD00" attach="left" box="[132,142,722,734]" fontSize="5" pageId="3" pageNumber="129">C</subScript>
|
||
110.5 (d, C-8) and 160.4 (s, C-9)]. The small value of
|
||
<emphasis id="B974EA88DF153F47A7853DEDFD20FD02" box="[679,686,712,732]" italics="true" pageId="3" pageNumber="129">J</emphasis>
|
||
<subScript id="178434DFDF153F47A78F3DF7FD4DFD00" attach="left" box="[685,707,722,734]" fontSize="5" pageId="3" pageNumber="129">3,4</subScript>
|
||
=1.8 Hz indicated that H-4 was
|
||
<emphasis id="B974EA88DF153F47A4753DC1FEFEFD26" box="[343,368,740,760]" italics="true" pageId="3" pageNumber="129">cis</emphasis>
|
||
to H-3, while the large value of
|
||
<emphasis id="B974EA88DF153F47A7853DC1FD20FD26" box="[679,686,740,760]" italics="true" pageId="3" pageNumber="129">J</emphasis>
|
||
<subScript id="178434DFDF153F47A78F3DCBFD4AFD24" attach="left" box="[685,708,750,762]" fontSize="5" pageId="3" pageNumber="129">2,3</subScript>
|
||
=9.5 Hz supported a
|
||
<emphasis id="B974EA88DF153F47A5CE3C25FE93FCCA" box="[236,285,768,788]" italics="true" pageId="3" pageNumber="129">trans</emphasis>
|
||
quasi-diaxial orientation of H-2 and H-3. In accordance with modeling studies (
|
||
<emphasis id="B974EA88DF153F47A48B3C39FD88FCEE" box="[425,518,796,816]" italics="true" pageId="3" pageNumber="129">vide infra</emphasis>
|
||
), in the minimum energy conformation
|
||
<emphasis id="B974EA88DF153F47A4203C1CFEA6FC92" bold="true" box="[258,296,825,844]" pageId="3" pageNumber="129">13a</emphasis>
|
||
(
|
||
<figureCitation id="133B2A1FDF153F47A41A3C1CFEFFFC92" box="[312,369,825,844]" captionStart="Fig" captionStartId="4.[87,113,1873,1887]" captionTargetBox="[397,1159,203,1843]" captionTargetId="figure-5@4.[369,1179,155,1792]" captionTargetPageId="4" captionText="Fig. 5. Modeled minimum energy conformations of compounds 13, 14oi, 14ƥ, 15oi, and 15ƥ. The calculated characteristic torsional angles Ʈ1 (C11–C1–C2–C3) and Ʈ (C11–C10–C9–C8) are reported under each conformer. The relative energy (kcalmol —1) and relative abundances of each pair of conformers in dichloromethane at room 2 temperature are reported between brackets." figureDoi="http://doi.org/10.5281/zenodo.10491078" httpUri="https://zenodo.org/record/10491078/files/figure.png" pageId="3" pageNumber="129">Fig. 5</figureCitation>
|
||
), the OH-4 and Me-3 groups were thus pseudo-axially and pseudo-equatorially oriented, respectively, on the central cycloheptadiene ring. The HMBC spectrum (
|
||
<figureCitation id="133B2A1FDF153F47A7B43C55FD58FC5A" box="[662,726,880,900]" captionStart="Fig" captionStartId="3.[462,488,1567,1581]" captionTargetBox="[378,1175,1172,1548]" captionTargetId="graphics-774@3.[852,1156,1186,1488]" captionTargetPageId="3" captionText="Fig. 3. Characteristic HMBC (a) and NOESY correlations (b) of russulanobiline B (13)." figureDoi="http://doi.org/10.5281/zenodo.10491074" httpUri="https://zenodo.org/record/10491074/files/figure.png" pageId="3" pageNumber="129">Fig. 3a</figureCitation>
|
||
) confirmed signal assignments and structure
|
||
<emphasis id="B974EA88DF153F47A72A3CA9FDAFFC41" bold="true" box="[520,545,908,927]" pageId="3" pageNumber="129">13</emphasis>
|
||
, while the NOESY spectrum (
|
||
<figureCitation id="133B2A1FDF153F47A5903C8DFF7AFC65" box="[178,244,936,956]" captionStart="Fig" captionStartId="3.[462,488,1567,1581]" captionTargetBox="[378,1175,1172,1548]" captionTargetId="graphics-774@3.[852,1156,1186,1488]" captionTargetPageId="3" captionText="Fig. 3. Characteristic HMBC (a) and NOESY correlations (b) of russulanobiline B (13)." figureDoi="http://doi.org/10.5281/zenodo.10491074" httpUri="https://zenodo.org/record/10491074/files/figure.png" pageId="3" pageNumber="129">Fig. 3b</figureCitation>
|
||
) supported its relative stereochemistry. In addition, a NOESY cross peak (
|
||
<figureCitation id="133B2A1FDF153F47A40D3CE1FEFEFC09" box="[303,368,964,983]" captionStart="Fig" captionStartId="3.[462,488,1567,1581]" captionTargetBox="[378,1175,1172,1548]" captionTargetId="graphics-774@3.[852,1156,1186,1488]" captionTargetPageId="3" captionText="Fig. 3. Characteristic HMBC (a) and NOESY correlations (b) of russulanobiline B (13)." figureDoi="http://doi.org/10.5281/zenodo.10491074" httpUri="https://zenodo.org/record/10491074/files/figure.png" pageId="3" pageNumber="129">Fig. 3b</figureCitation>
|
||
) between the oxygenated proton H-4 and
|
||
<subScript id="178434DFDF153F47A5533CC4FF1CFC2D" attach="right" box="[113,146,992,1014]" fontSize="5" pageId="3" pageNumber="129">Hβ-</subScript>
|
||
5 of compound
|
||
<emphasis id="B974EA88DF153F47A40D3CC5FEC6FC2D" bold="true" box="[303,328,992,1011]" pageId="3" pageNumber="129">13</emphasis>
|
||
confirmed the position of the lactone methylene group at C-5 and, as a consequence, the carbonyl group at C-13.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF153F47A5B33B3DFC81FBA1" blockId="3.[113,784,712,1151]" pageId="3" pageNumber="129">
|
||
Inspection of the NMR spectra of russulanobiline C-
|
||
<emphasis id="B974EA88DF153F47A7883B3DFD4DFBF5" bold="true" box="[682,707,1048,1067]" pageId="3" pageNumber="129">14</emphasis>
|
||
clearly indicated the close structural relationship with compound
|
||
<emphasis id="B974EA88DF153F47A7CC3B11FC89FB99" bold="true" box="[750,775,1076,1095]" pageId="3" pageNumber="129">13</emphasis>
|
||
; however, the majority of the
|
||
<superScript id="7C759BD2DF153F47A48B3B69FE32FB86" attach="right" box="[425,444,1100,1112]" fontSize="5" pageId="3" pageNumber="129">13</superScript>
|
||
C NMR resonances were splitted into two signals due to the presence of two C-5 epimers (
|
||
<emphasis id="B974EA88DF153F47A7853B4FFC8FFBA0" box="[679,769,1130,1150]" italics="true" pageId="3" pageNumber="129">vide infra</emphasis>
|
||
).
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF153F47A61D3F93FAF8FC2C" blockId="3.[831,1501,182,1150]" pageId="3" pageNumber="129">
|
||
<materialsCitation id="3B683CC7DF153F47A61D3F93FAFCFC2C" collectionCode="AB, NMR, HMBC, NOESY" latitude="-170.9" pageId="3" pageNumber="129" specimenCount="1">
|
||
Actually, the compound contained: (i) a lactone carbonyl group (
|
||
<emphasis id="B974EA88DF153F47A6653FF7FCDCFF3B" box="[839,850,210,229]" italics="true" pageId="3" pageNumber="129">δ</emphasis>
|
||
<subScript id="178434DFDF153F47A6703FFEFCD2FF39" attach="left" box="[850,860,219,231]" fontSize="5" pageId="3" pageNumber="129">C</subScript>
|
||
<geoCoordinate id="EE34505DDF153F47A6463FF7FC29FF3B" box="[868,935,210,229]" degrees="169.7" direction="south" orientation="latitude" pageId="3" pageNumber="129" precision="5555" value="-169.7">169.7s</geoCoordinate>
|
||
), cross-conjugated with a 1,3-diene moiety (
|
||
<emphasis id="B974EA88DF153F47A0543FF7FA0FFF3B" box="[1398,1409,210,229]" italics="true" pageId="3" pageNumber="129">δ</emphasis>
|
||
<subScript id="178434DFDF153F47A0A33FFEFA05FF39" attach="left" box="[1409,1419,219,231]" fontSize="5" pageId="3" pageNumber="129">C</subScript>
|
||
<geoCoordinate id="EE34505DDF153F47A0B13FF7FA5AFF3B" box="[1427,1492,210,229]" degrees="144.5" direction="south" orientation="latitude" pageId="3" pageNumber="129" precision="5555" value="-144.5">144.5s</geoCoordinate>
|
||
/
|
||
<geoCoordinate id="EE34505DDF153F47A61D3FCBFC0FFEDF" box="[831,897,238,257]" degrees="144.4" direction="south" orientation="latitude" pageId="3" pageNumber="129" precision="5555" value="-144.4">144.4s</geoCoordinate>
|
||
,
|
||
<geoCoordinate id="EE34505DDF153F47A6B33FCBFC5DFEDF" box="[913,979,238,257]" degrees="135.2" direction="south" orientation="latitude" pageId="3" pageNumber="129" precision="5555" value="-135.2">135.2s</geoCoordinate>
|
||
/
|
||
<geoCoordinate id="EE34505DDF153F47A6FE3FCBFB93FEDF" box="[988,1053,238,257]" degrees="135.1" direction="south" orientation="latitude" pageId="3" pageNumber="129" precision="5555" value="-135.1">135.1s</geoCoordinate>
|
||
, 112.8d/112.3d,
|
||
<geoCoordinate id="EE34505DDF153F47A1EC3FCBFA80FEDF" box="[1230,1294,238,257]" degrees="171.1" direction="south" orientation="latitude" pageId="3" pageNumber="129" precision="5555" value="-171.1">171.1s</geoCoordinate>
|
||
/
|
||
<geoCoordinate id="EE34505DDF153F47A0353FCBFAD7FEDF" box="[1303,1369,238,257]" degrees="170.9" direction="south" orientation="latitude" pageId="3" pageNumber="129" precision="5555" value="-170.9">170.9s</geoCoordinate>
|
||
) comprising the C
|
||
<subScript id="178434DFDF153F47A6563E36FCF3FEC1" attach="left" box="[884,893,275,287]" fontSize="5" pageId="3" pageNumber="129">6</subScript>
|
||
–C
|
||
<subScript id="178434DFDF153F47A6B53E36FC2EFEC1" attach="left" box="[919,928,275,287]" fontSize="5" pageId="3" pageNumber="129">7</subScript>
|
||
–C
|
||
<subScript id="178434DFDF153F47A6993E36FC4AFEC1" attach="left" box="[955,964,275,287]" fontSize="5" pageId="3" pageNumber="129">8</subScript>
|
||
–C
|
||
<subScript id="178434DFDF153F47A6FC3E36FC69FEC1" attach="left" box="[990,999,275,287]" fontSize="5" pageId="3" pageNumber="129">9</subScript>
|
||
carbon sequence; (ii) a vinylic proton at C-8 (
|
||
<emphasis id="B974EA88DF153F47A0E73E2FFA5EFEC3" box="[1477,1488,266,285]" italics="true" pageId="3" pageNumber="129">δ</emphasis>
|
||
<subScript id="178434DFDF153F47A0F23E36FA52FEC1" attach="left" box="[1488,1500,275,287]" fontSize="5" pageId="3" pageNumber="129">H</subScript>
|
||
6.43/6.39, br s) allylically coupled to
|
||
<subScript id="178434DFDF153F47A18C3E03FB41FEE7" attach="left" box="[1198,1231,294,315]" fontSize="5" pageId="3" pageNumber="129">Hβ-</subScript>
|
||
10 (
|
||
<emphasis id="B974EA88DF153F47A1D43E03FA8FFEE7" box="[1270,1281,294,313]" italics="true" pageId="3" pageNumber="129">δ</emphasis>
|
||
<subScript id="178434DFDF153F47A0233E0AFA83FEE5" attach="left" box="[1281,1293,303,315]" fontSize="5" pageId="3" pageNumber="129">H</subScript>
|
||
2.56), which formed a broad AB system (
|
||
<emphasis id="B974EA88DF153F47A12B3E64FB9EFE8B" box="[1033,1040,321,341]" italics="true" pageId="3" pageNumber="129">J</emphasis>
|
||
<subScript id="178434DFDF153F47A1323E6EFBAAFE89" attach="left" box="[1040,1060,331,343]" fontSize="5" pageId="3" pageNumber="129">
|
||
<collectionCode id="ED11AE5FDF153F47A1323E6EFBAAFE89" box="[1040,1060,331,343]" pageId="3" pageNumber="129">AB</collectionCode>
|
||
</subScript>
|
||
= 17.2 Hz) with
|
||
<subScript id="178434DFDF153F47A1E83E67FB63FE8B" attach="left" box="[1226,1261,322,344]" fontSize="7" pageId="3" pageNumber="129">Hoi-</subScript>
|
||
10 (
|
||
<emphasis id="B974EA88DF153F47A0343E67FAAFFE8B" box="[1302,1313,322,341]" italics="true" pageId="3" pageNumber="129">δ</emphasis>
|
||
<subScript id="178434DFDF153F47A0033E6EFAA3FE89" attach="left" box="[1313,1325,331,343]" fontSize="5" pageId="3" pageNumber="129">H</subScript>
|
||
2.50); (iii) a proton spin system extending from H
|
||
<subScript id="178434DFDF153F47A1B73E42FB10FEAD" attach="right" box="[1173,1182,359,371]" fontSize="5" pageId="3" pageNumber="129">2</subScript>
|
||
-1 to H
|
||
<subScript id="178434DFDF153F47A1C63E42FB63FEAD" attach="left" box="[1252,1261,359,371]" fontSize="5" pageId="3" pageNumber="129">3</subScript>
|
||
-12 through H-2 and H- 3. Moreover, the presence, in the
|
||
<superScript id="7C759BD2DF153F47A1AF3E53FB2EFE5C" attach="right" box="[1165,1184,374,386]" fontSize="5" pageId="3" pageNumber="129">13</superScript>
|
||
C
|
||
<collectionCode id="ED11AE5FDF153F47A1913E5FFB6BFE53" box="[1203,1253,378,397]" country="Netherlands" httpUri="http://grbio.org/cool/jyde-k516" name="Natuurhistorisch Museum" pageId="3" pageNumber="129">NMR</collectionCode>
|
||
spectrum of
|
||
<emphasis id="B974EA88DF153F47A04A3E5CFA0FFE52" bold="true" box="[1384,1409,377,396]" pageId="3" pageNumber="129">14</emphasis>
|
||
, of a signal (
|
||
<emphasis id="B974EA88DF153F47A64E3EB3FCF9FE77" box="[876,887,406,425]" italics="true" pageId="3" pageNumber="129">δ</emphasis>
|
||
<subScript id="178434DFDF153F47A6553EBBFC0FFE74" attach="left" box="[887,897,414,426]" fontSize="5" pageId="3" pageNumber="129">C</subScript>
|
||
198.3s/198.1s) assignable to an unsaturated carbonyl group and the absence of signals attributable to H-4/C-4, clearly indicated the presence of a ketone at C-4. This assignment was confirmed by the
|
||
<collectionCode id="ED11AE5FDF153F47A6473ECCFC2AFE22" box="[869,932,489,508]" pageId="3" pageNumber="129">HMBC</collectionCode>
|
||
cross-peak correlation (
|
||
<figureCitation id="133B2A1FDF153F47A1B53ECCFB57FE22" box="[1175,1241,489,508]" captionStart="Fig" captionStartId="3.[462,488,1999,2013]" captionTargetBox="[431,1178,1668,1967]" captionTargetPageId="3" captionText="Fig. 4. Characteristic HMBC (a) and NOESY correlations (b) of russulanobiline C (14)." figureDoi="http://doi.org/10.5281/zenodo.10491076" httpUri="https://zenodo.org/record/10491076/files/figure.png" pageId="3" pageNumber="129">Fig. 4a</figureCitation>
|
||
) between H
|
||
<subScript id="178434DFDF153F47A0713ED7FAD2FE20" attach="right" box="[1363,1372,498,510]" fontSize="5" pageId="3" pageNumber="129">3</subScript>
|
||
-12 (
|
||
<emphasis id="B974EA88DF153F47A0AE3ECCFA19FE22" box="[1420,1431,489,508]" italics="true" pageId="3" pageNumber="129">δ</emphasis>
|
||
<subScript id="178434DFDF153F47A0B53ED7FA2DFE20" attach="left" box="[1431,1443,498,510]" fontSize="5" pageId="3" pageNumber="129">H</subScript>
|
||
1.12) and the ketone carbonyl carbon. Accordingly, compared to the corresponding signal of alcohol
|
||
<emphasis id="B974EA88DF153F47A1493D04FB0AFDEA" bold="true" box="[1131,1156,545,564]" pageId="3" pageNumber="129">13</emphasis>
|
||
, proton H-
|
||
<quantity id="4CF89B7FDF153F47A1D83D04FAACFDEA" box="[1274,1314,545,564]" metricMagnitude="-2" metricUnit="m" metricValue="7.62" pageId="3" pageNumber="129" unit="in" value="3.0">3 in</quantity>
|
||
russulanobiline C lacked the vicinal coupling constant with H-4 and it was significantly shifted downfield from
|
||
<emphasis id="B974EA88DF153F47A14C3D7CFBF7FDB2" box="[1134,1145,601,620]" italics="true" pageId="3" pageNumber="129">δ</emphasis>
|
||
<subScript id="178434DFDF153F47A15B3D47FB0BFDB0" attach="left" box="[1145,1157,610,622]" fontSize="5" pageId="3" pageNumber="129">H</subScript>
|
||
1.86 to
|
||
<emphasis id="B974EA88DF153F47A1F73D7CFB6EFDB2" box="[1237,1248,601,620]" italics="true" pageId="3" pageNumber="129">δ</emphasis>
|
||
<subScript id="178434DFDF153F47A1C23D47FB62FDB0" attach="left" box="[1248,1260,610,622]" fontSize="5" pageId="3" pageNumber="129">H</subScript>
|
||
2.75, due to the oi- position of the carbonyl group. In addition, two singlets for an acetal proton at
|
||
<emphasis id="B974EA88DF153F47A6863DB4FC21FD7A" box="[932,943,657,676]" italics="true" pageId="3" pageNumber="129">δ</emphasis>
|
||
<subScript id="178434DFDF153F47A68D3DBFFC35FD78" attach="left" box="[943,955,666,678]" fontSize="5" pageId="3" pageNumber="129">H</subScript>
|
||
6.46/
|
||
<quantity id="4CF89B7FDF153F47A6D73DB4FBB2FD7A" box="[1013,1084,657,676]" metricMagnitude="-1" metricUnit="m" metricValue="1.61798" pageId="3" pageNumber="129" unit="in" value="6.37">6.37 in</quantity>
|
||
the
|
||
<superScript id="7C759BD2DF153F47A1493DA8FBFAFD47" attach="right" box="[1131,1140,653,665]" fontSize="5" pageId="3" pageNumber="129">1</superScript>
|
||
H
|
||
<collectionCode id="ED11AE5FDF153F47A1A93DB4FB33FD7A" box="[1163,1213,657,676]" country="Netherlands" httpUri="http://grbio.org/cool/jyde-k516" name="Natuurhistorisch Museum" pageId="3" pageNumber="129">NMR</collectionCode>
|
||
spectrum and two doublets for an acetal carbon at
|
||
<emphasis id="B974EA88DF153F47A1023D88FBA5FD1E" box="[1056,1067,685,704]" italics="true" pageId="3" pageNumber="129">δ</emphasis>
|
||
<subScript id="178434DFDF153F47A1093D90FBBBFD1F" attach="left" box="[1067,1077,693,705]" fontSize="5" pageId="3" pageNumber="129">C</subScript>
|
||
97.1/97.0 in the
|
||
<superScript id="7C759BD2DF153F47A1F93D8CFB60FD6B" attach="right" box="[1243,1262,681,693]" fontSize="5" pageId="3" pageNumber="129">13</superScript>
|
||
C
|
||
<collectionCode id="ED11AE5FDF153F47A0223D88FABCFD1E" box="[1280,1330,685,704]" country="Netherlands" httpUri="http://grbio.org/cool/jyde-k516" name="Natuurhistorisch Museum" pageId="3" pageNumber="129">NMR</collectionCode>
|
||
spectrum of russulanobiline C, suggested that compound
|
||
<emphasis id="B974EA88DF153F47A0323DEDFAA7FD05" bold="true" box="[1296,1321,712,731]" pageId="3" pageNumber="129">14</emphasis>
|
||
contained a Ƴ- hydroxybutenolide moiety. Thirteen pairs of peaks with similar height and chemical shift values in the
|
||
<superScript id="7C759BD2DF153F47A02F3DD9FAAEFCD6" attach="right" box="[1293,1312,764,776]" fontSize="5" pageId="3" pageNumber="129">13</superScript>
|
||
C
|
||
<collectionCode id="ED11AE5FDF153F47A01E3C24FAE0FCCA" box="[1340,1390,769,788]" country="Netherlands" httpUri="http://grbio.org/cool/jyde-k516" name="Natuurhistorisch Museum" pageId="3" pageNumber="129">NMR</collectionCode>
|
||
spectrum indicated that russulanobiline C was constituted by two epimers,
|
||
<emphasis id="B974EA88DF153F47A61D3C1DFCE8FC92" bold="true" box="[831,870,821,844]" pageId="3" pageNumber="129">14oi</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF153F47A6BD3C1DFC4AFC95" bold="true" box="[927,964,824,843]" pageId="3" pageNumber="129">14ƥ</emphasis>
|
||
, at the carbinol center of the Ƴ- hydroxybutenolide unit, in a ratio of ca. 1:1. The fast equilibrium between the two epimers made the chromatographic separation of the mixture impossible.
|
||
<collectionCode id="ED11AE5FDF153F47A69A3CA9FC79FC41" box="[952,1015,908,927]" pageId="3" pageNumber="129">HMBC</collectionCode>
|
||
(
|
||
<figureCitation id="133B2A1FDF153F47A12A3CAEFBC5FC41" box="[1032,1099,907,927]" captionStart="Fig" captionStartId="3.[462,488,1999,2013]" captionTargetBox="[431,1178,1668,1967]" captionTargetPageId="3" captionText="Fig. 4. Characteristic HMBC (a) and NOESY correlations (b) of russulanobiline C (14)." figureDoi="http://doi.org/10.5281/zenodo.10491076" httpUri="https://zenodo.org/record/10491076/files/figure.png" pageId="3" pageNumber="129">Fig. 4a</figureCitation>
|
||
) and
|
||
<collectionCode id="ED11AE5FDF153F47A1A53CA9FB42FC41" box="[1159,1228,908,927]" pageId="3" pageNumber="129">NOESY</collectionCode>
|
||
correlations (
|
||
<figureCitation id="133B2A1FDF153F47A07E3CAEFA2EFC40" box="[1372,1440,907,927]" captionStart="Fig" captionStartId="3.[462,488,1999,2013]" captionTargetBox="[431,1178,1668,1967]" captionTargetPageId="3" captionText="Fig. 4. Characteristic HMBC (a) and NOESY correlations (b) of russulanobiline C (14)." figureDoi="http://doi.org/10.5281/zenodo.10491076" httpUri="https://zenodo.org/record/10491076/files/figure.png" pageId="3" pageNumber="129">Fig. 4b</figureCitation>
|
||
) supported the gross structure of russulanobiline C, including its relative stereochemistry; however, assignment of the
|
||
<collectionCode id="ED11AE5FDF153F47A0883CE1FA52FC09" box="[1450,1500,964,983]" country="Netherlands" httpUri="http://grbio.org/cool/jyde-k516" name="Natuurhistorisch Museum" pageId="3" pageNumber="129">NMR</collectionCode>
|
||
resonances to each of the two anomers was impossible
|
||
</materialsCitation>
|
||
.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF153F47A67C3CDEFA53FBA0" blockId="3.[831,1501,182,1150]" pageId="3" pageNumber="129">
|
||
<materialsCitation id="3B683CC7DF153F47A67C3CDEFA53FBA0" collectionCode="NMR" pageId="3" pageNumber="129" specimenCount="15">
|
||
The sole 2D
|
||
<collectionCode id="ED11AE5FDF153F47A6FE3CD9FB80FBD1" box="[988,1038,1020,1039]" country="Netherlands" httpUri="http://grbio.org/cool/jyde-k516" name="Natuurhistorisch Museum" pageId="3" pageNumber="129">NMR</collectionCode>
|
||
data did not allow us to make a firm distinction between the alternative regioisomeric structures
|
||
<emphasis id="B974EA88DF153F47A07C3B32FA3FFBF4" bold="true" box="[1374,1457,1044,1067]" pageId="3" pageNumber="129">14oi/14ƥ</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF153F47A61D3B16FC1FFB98" bold="true" box="[831,913,1072,1095]" pageId="3" pageNumber="129">
|
||
15oi/
|
||
<specimenCount id="9D06FD13DF153F47A64D3B16FC1FFB98" box="[879,913,1075,1094]" count="15" pageId="3" pageNumber="129" type="generic">15ƥ</specimenCount>
|
||
</emphasis>
|
||
. Since a crystal suitable for X-ray of russulanobiline C was not available, we envisaged the possibility to distinguish the two regioisomers by comparing the experimental
|
||
<superScript id="7C759BD2DF153F47A02F3B42FAAEFBAD" attach="right" box="[1293,1312,1127,1139]" fontSize="5" pageId="3" pageNumber="129">13</superScript>
|
||
C
|
||
<collectionCode id="ED11AE5FDF153F47A0163B4EFAE8FBA0" box="[1332,1382,1131,1150]" country="Netherlands" httpUri="http://grbio.org/cool/jyde-k516" name="Natuurhistorisch Museum" pageId="3" pageNumber="129">NMR</collectionCode>
|
||
resonances
|
||
</materialsCitation>
|
||
</paragraph>
|
||
<caption id="DF7F6612DF153F47A4EC393AFB0FF9F3" ID-DOI="http://doi.org/10.5281/zenodo.10491074" ID-Zenodo-Dep="10491074" box="[462,1153,1567,1581]" httpUri="https://zenodo.org/record/10491074/files/figure.png" pageId="3" pageNumber="129" startId="3.[462,488,1567,1581]" targetBox="[378,1175,1172,1548]" targetPageId="3" targetType="figure">
|
||
<paragraph id="8BBF369ADF153F47A4EC393AFB0FF9F3" blockId="3.[462,1153,1567,1581]" box="[462,1153,1567,1581]" pageId="3" pageNumber="129">
|
||
<emphasis id="B974EA88DF153F47A4EC393AFD8EF9F3" bold="true" box="[462,512,1567,1581]" pageId="3" pageNumber="129">Fig. 3.</emphasis>
|
||
Characteristic HMBC (a) and NOESY correlations (b) of russulanobiline B (
|
||
<emphasis id="B974EA88DF153F47A143393AFBFBF9F3" bold="true" box="[1121,1141,1567,1581]" pageId="3" pageNumber="129">13</emphasis>
|
||
).
|
||
</paragraph>
|
||
</caption>
|
||
<caption id="DF7F6612DF153F47A4EC38EAFB0FF803" ID-DOI="http://doi.org/10.5281/zenodo.10491076" ID-Zenodo-Dep="10491076" box="[462,1153,1999,2013]" httpUri="https://zenodo.org/record/10491076/files/figure.png" pageId="3" pageNumber="129" startId="3.[462,488,1999,2013]" targetBox="[431,1178,1668,1967]" targetPageId="3" targetType="figure">
|
||
<paragraph id="8BBF369ADF153F47A4EC38EAFB0FF803" blockId="3.[462,1153,1999,2013]" box="[462,1153,1999,2013]" pageId="3" pageNumber="129">
|
||
<emphasis id="B974EA88DF153F47A4EC38EAFD8EF803" bold="true" box="[462,512,1999,2013]" pageId="3" pageNumber="129">Fig. 4.</emphasis>
|
||
Characteristic HMBC (a) and NOESY correlations (b) of russulanobiline C (
|
||
<emphasis id="B974EA88DF153F47A14338EAFBFBF803" bold="true" box="[1121,1141,1999,2013]" pageId="3" pageNumber="129">14</emphasis>
|
||
).
|
||
</paragraph>
|
||
</caption>
|
||
<caption id="DF7F6612DF123F40A5753874FE4EF853" ID-DOI="http://doi.org/10.5281/zenodo.10491078" ID-Zenodo-Dep="10491078" httpUri="https://zenodo.org/record/10491078/files/figure.png" pageId="4" pageNumber="130" startId="4.[87,113,1873,1887]" targetBox="[397,1159,203,1843]" targetPageId="4" targetType="figure">
|
||
<paragraph id="8BBF369ADF123F40A5753874FE4EF853" blockId="4.[87,1474,1870,1933]" pageId="4" pageNumber="130">
|
||
<emphasis id="B974EA88DF123F40A5753874FF03F881" bold="true" box="[87,141,1873,1887]" pageId="4" pageNumber="130">Fig. 5.</emphasis>
|
||
Modeled minimum energy conformations of compounds
|
||
<emphasis id="B974EA88DF123F40A75E3874FD1EF881" bold="true" box="[636,656,1873,1887]" pageId="4" pageNumber="130">13</emphasis>
|
||
,
|
||
<emphasis id="B974EA88DF123F40A7BC3874FD33F8BE" bold="true" box="[670,701,1870,1888]" pageId="4" pageNumber="130">14oi</emphasis>
|
||
,
|
||
<emphasis id="B974EA88DF123F40A7E93874FC9BF8BE" bold="true" box="[715,789,1870,1888]" pageId="4" pageNumber="130">14ƥ, 15oi</emphasis>
|
||
, and
|
||
<emphasis id="B974EA88DF123F40A6683874FCE9F8BE" bold="true" box="[842,871,1873,1888]" pageId="4" pageNumber="130">15ƥ</emphasis>
|
||
. The calculated characteristic torsional angles
|
||
<emphasis id="B974EA88DF123F40A1DA386AFA8FF8BF" box="[1272,1281,1871,1889]" italics="true" pageId="4" pageNumber="130">Ʈ</emphasis>
|
||
<subScript id="178434DFDF123F40A020387DFA87F8BC" attach="right" box="[1282,1289,1880,1890]" fontSize="4" pageId="4" pageNumber="130">1</subScript>
|
||
(C11–C1–C2–C3) and
|
||
<emphasis id="B974EA88DF123F40A5753840FFEEF8A9" box="[87,96,1893,1911]" italics="true" pageId="4" pageNumber="130">Ʈ</emphasis>
|
||
(C11–C10–C9–C8) are reported under each conformer. The relative energy (kcal mol
|
||
<superScript id="7C759BD2DF123F40A63A3841FCA7F8B0" attach="left" box="[792,809,1892,1902]" fontSize="4" pageId="4" pageNumber="130">
|
||
<emphasis id="B974EA88DF123F40A63A3841FCACF8B3" box="[792,802,1892,1901]" italics="true" pageId="4" pageNumber="130">—</emphasis>
|
||
1
|
||
</superScript>
|
||
) and relative abundances of each pair of conformers in dichloromethane at room
|
||
<subScript id="178434DFDF123F40A542384AFFE9F8A7" attach="right" box="[96,103,1903,1913]" fontSize="4" pageId="4" pageNumber="130">2</subScript>
|
||
temperature are reported between brackets.
|
||
</paragraph>
|
||
</caption>
|
||
<paragraph id="8BBF369ADF133F41A5533F93FC18FEDF" blockId="5.[113,783,182,341]" lastBlockId="5.[831,1501,180,341]" pageId="5" pageNumber="131">
|
||
of russulanobiline C with the chemical shifts calculated for the most populated modeled conformers of
|
||
<emphasis id="B974EA88DF133F41A7083FF7FDF2FF3B" bold="true" box="[554,636,208,231]" pageId="5" pageNumber="131">14oi/14ƥ</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF133F41A79E3FF7FC81FF3B" bold="true" box="[700,783,208,231]" pageId="5" pageNumber="131">15oi/15ƥ</emphasis>
|
||
(
|
||
<tableCitation id="C6820321DF133F41A5583FCBFF4CFEDF" box="[122,194,238,257]" captionStart="Table 1" captionStartId="2.[87,131,183,197]" captionText="Table 1 Experimental (75.47 MHz, CD Cl) 13C NMR resonances (δ) for compound 7a and russulanobilines A–C, and calculated 13C NMR resonances (δ) for structures 13a, 14oia, 14ƥa, 2 2 C C 15oia, and 15ƥa." pageId="5" pageNumber="131">Table 1</tableCitation>
|
||
). To confirm the validity of the method, the related lactone russulanobiline B (
|
||
<emphasis id="B974EA88DF133F41A4173E2FFEC0FEC3" bold="true" box="[309,334,266,285]" pageId="5" pageNumber="131">13</emphasis>
|
||
) was also modeled and the calculated
|
||
<superScript id="7C759BD2DF133F41A7CD3E23FC8CFECC" attach="right" box="[751,770,262,274]" fontSize="5" pageId="5" pageNumber="131">13</superScript>
|
||
C NMR signals were compared with the experimental spectrum (
|
||
<tableCitation id="C6820321DF133F41A5583E67FF4AFE8B" box="[122,196,322,341]" captionStart="Table 1" captionStartId="2.[87,131,183,197]" captionText="Table 1 Experimental (75.47 MHz, CD Cl) 13C NMR resonances (δ) for compound 7a and russulanobilines A–C, and calculated 13C NMR resonances (δ) for structures 13a, 14oia, 14ƥa, 2 2 C C 15oia, and 15ƥa." pageId="5" pageNumber="131">Table 1</tableCitation>
|
||
). carbons for the regioisomeric structures
|
||
<emphasis id="B974EA88DF133F41A1D73F93FAC9FF17" bold="true" box="[1269,1351,180,203]" pageId="5" pageNumber="131">14oi/14ƥ</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF133F41A0A73F93FA59FF17" bold="true" box="[1413,1495,180,203]" pageId="5" pageNumber="131">15oi/15ƥ</emphasis>
|
||
, clearly showed a much better correspondence with structures
|
||
<emphasis id="B974EA88DF133F41A61D3FCBFC1FFEDF" bold="true" box="[831,913,236,259]" pageId="5" pageNumber="131">
|
||
14oi/
|
||
<specimenCount id="9D06FD13DF133F41A64D3FCBFC1FFEDF" box="[879,913,238,257]" count="14" pageId="5" pageNumber="131" type="generic">14ƥ</specimenCount>
|
||
</emphasis>
|
||
.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF133F41A67C3E2FFAB3FE8B" blockId="5.[831,1501,180,341]" pageId="5" pageNumber="131">
|
||
In conclusion, on the basis of the modeling studies and
|
||
<superScript id="7C759BD2DF133F41A0A73E23FA16FECC" attach="right" box="[1413,1432,262,274]" fontSize="5" pageId="5" pageNumber="131">13</superScript>
|
||
C NMR chemical shift calculations, we confidently assigned structure
|
||
<emphasis id="B974EA88DF133F41A09C3E03FA59FEE7" bold="true" box="[1470,1495,294,313]" pageId="5" pageNumber="131">14</emphasis>
|
||
, as a mixture of C-5 anomers, to russulanobiline C.
|
||
</paragraph>
|
||
<subSection id="E28F2F71DF133F41A5503BA1FC81F803" pageId="5" pageNumber="131" type="multiple">
|
||
<paragraph id="8BBF369ADF133F41A5503BA1FC8DFB46" blockId="5.[114,771,1152,1176]" box="[114,771,1152,1176]" pageId="5" pageNumber="131">
|
||
<heading id="D0F781F6DF133F41A5503BA1FC8DFB46" box="[114,771,1152,1176]" centered="true" fontSize="36" level="2" pageId="5" pageNumber="131" reason="3">
|
||
<emphasis id="B974EA88DF133F41A5503BA1FC8DFB46" box="[114,771,1152,1176]" italics="true" pageId="5" pageNumber="131">
|
||
2.3. Modeling studies and
|
||
<superScript id="7C759BD2DF133F41A4523BA5FE0CFB53" attach="right" box="[368,386,1152,1165]" fontSize="5" pageId="5" pageNumber="131">13</superScript>
|
||
C
|
||
<collectionCode id="ED11AE5FDF133F41A4B73BA1FE4AFB46" box="[405,452,1156,1176]" country="Netherlands" httpUri="http://grbio.org/cool/jyde-k516" name="Natuurhistorisch Museum" pageId="5" pageNumber="131">NMR</collectionCode>
|
||
calculations of structures
|
||
<emphasis id="B974EA88DF133F41A7E13BA1FC8DFB46" bold="true" box="[707,771,1156,1176]" italics="true" pageId="5" pageNumber="131">13–15</emphasis>
|
||
</emphasis>
|
||
</heading>
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF133F41A5B33B98FF5EF918" blockId="5.[113,783,1213,2013]" pageId="5" pageNumber="131">
|
||
All the degrees of conformational freedom were considered for the structures
|
||
<emphasis id="B974EA88DF133F41A4253BFCFEAEFB32" bold="true" box="[263,288,1241,1260]" pageId="5" pageNumber="131">13</emphasis>
|
||
,
|
||
<emphasis id="B974EA88DF133F41A40F3BFCFE0AFB32" bold="true" box="[301,388,1238,1261]" pageId="5" pageNumber="131">14oi/14ƥ,</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF133F41A49B3BFCFD82FB32" bold="true" box="[441,524,1238,1261]" pageId="5" pageNumber="131">15oi/15ƥ</emphasis>
|
||
, in particular the various possible conformations of cyclopentane ring and the orientation of the methyl groups H
|
||
<subScript id="178434DFDF133F41A44F3A3FFEF8FAF8" attach="left" box="[365,374,1306,1318]" fontSize="5" pageId="5" pageNumber="131">3</subScript>
|
||
-14 and H
|
||
<subScript id="178434DFDF133F41A4C63A3FFE63FAF8" attach="left" box="[484,493,1306,1318]" fontSize="5" pageId="5" pageNumber="131">3</subScript>
|
||
-15. Each structure showed two mainly populated conformations
|
||
<emphasis id="B974EA88DF133F41A7283A09FDBEFAE1" bold="true" box="[522,560,1324,1343]" pageId="5" pageNumber="131">13a</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF133F41A74D3A09FD18FAE1" bold="true" box="[623,662,1324,1343]" pageId="5" pageNumber="131">13b</emphasis>
|
||
,
|
||
<emphasis id="B974EA88DF133F41A78A3A09FD52FA9E" bold="true" box="[680,732,1322,1345]" pageId="5" pageNumber="131">14oia</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF133F41A5533A6DFF28FA85" bold="true" box="[113,166,1350,1373]" pageId="5" pageNumber="131">14oib</emphasis>
|
||
,
|
||
<emphasis id="B974EA88DF133F41A5943A6DFF69FA85" bold="true" box="[182,231,1352,1371]" pageId="5" pageNumber="131">14ƥa</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF133F41A4003A6DFEDDFA85" bold="true" box="[290,339,1352,1371]" pageId="5" pageNumber="131">14ƥb</emphasis>
|
||
,
|
||
<emphasis id="B974EA88DF133F41A4413A6DFE19FA85" bold="true" box="[355,407,1350,1373]" pageId="5" pageNumber="131">15oia</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF133F41A4F03A6DFD89FA85" bold="true" box="[466,519,1350,1373]" pageId="5" pageNumber="131">15oib</emphasis>
|
||
,
|
||
<emphasis id="B974EA88DF133F41A7353A6DFDC6FA85" bold="true" box="[535,584,1352,1371]" pageId="5" pageNumber="131">15ƥa</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF133F41A7A13A6DFD3AFA85" bold="true" box="[643,692,1352,1371]" pageId="5" pageNumber="131">15ƥb</emphasis>
|
||
(
|
||
<figureCitation id="133B2A1FDF133F41A7EA3A6DFC8CFA85" box="[712,770,1352,1371]" captionStart="Fig" captionStartId="4.[87,113,1873,1887]" captionTargetBox="[397,1159,203,1843]" captionTargetId="figure-5@4.[369,1179,155,1792]" captionTargetPageId="4" captionText="Fig. 5. Modeled minimum energy conformations of compounds 13, 14oi, 14ƥ, 15oi, and 15ƥ. The calculated characteristic torsional angles Ʈ1 (C11–C1–C2–C3) and Ʈ (C11–C10–C9–C8) are reported under each conformer. The relative energy (kcalmol —1) and relative abundances of each pair of conformers in dichloromethane at room 2 temperature are reported between brackets." figureDoi="http://doi.org/10.5281/zenodo.10491078" httpUri="https://zenodo.org/record/10491078/files/figure.png" pageId="5" pageNumber="131">Fig. 5</figureCitation>
|
||
), respectively, corresponding to two different geometries of the cyclopentane ring, characterized by the torsional angles
|
||
<emphasis id="B974EA88DF133F41A7D83A5AFC8BFA4A" box="[762,773,1407,1428]" italics="true" pageId="5" pageNumber="131">Ʈ</emphasis>
|
||
<subScript id="178434DFDF133F41A6243AACFC81FA4B" attach="right" box="[774,783,1417,1429]" fontSize="5" pageId="5" pageNumber="131">1</subScript>
|
||
(C11
|
||
<emphasis id="B974EA88DF133F41A5823ABBFF3CFA71" bold="true" box="[160,178,1438,1455]" pageId="5" pageNumber="131">A</emphasis>
|
||
C1
|
||
<emphasis id="B974EA88DF133F41A5EE3ABBFF50FA71" bold="true" box="[204,222,1438,1455]" pageId="5" pageNumber="131">A</emphasis>
|
||
C2
|
||
<emphasis id="B974EA88DF133F41A5D53ABBFE87FA71" bold="true" box="[247,265,1438,1455]" pageId="5" pageNumber="131">A</emphasis>
|
||
C3) and
|
||
<emphasis id="B974EA88DF133F41A4443ABEFEFFFA6E" box="[358,369,1435,1456]" italics="true" pageId="5" pageNumber="131">Ʈ</emphasis>
|
||
<subScript id="178434DFDF133F41A4503A80FEF5FA6F" attach="right" box="[370,379,1445,1457]" fontSize="5" pageId="5" pageNumber="131">2</subScript>
|
||
(C11
|
||
<emphasis id="B974EA88DF133F41A4973ABBFE49FA71" bold="true" box="[437,455,1438,1455]" pageId="5" pageNumber="131">A</emphasis>
|
||
C10
|
||
<emphasis id="B974EA88DF133F41A4CF3ABBFE71FA71" bold="true" box="[493,511,1438,1455]" pageId="5" pageNumber="131">A</emphasis>
|
||
C9
|
||
<emphasis id="B974EA88DF133F41A73B3ABBFDA5FA71" bold="true" box="[537,555,1438,1455]" pageId="5" pageNumber="131">A</emphasis>
|
||
C8) (
|
||
<figureCitation id="133B2A1FDF133F41A77D3AB9FD14FA71" box="[607,666,1436,1455]" captionStart="Fig" captionStartId="3.[462,488,1567,1581]" captionTargetBox="[378,1175,1172,1548]" captionTargetId="graphics-774@3.[852,1156,1186,1488]" captionTargetPageId="3" captionText="Fig. 3. Characteristic HMBC (a) and NOESY correlations (b) of russulanobiline B (13)." figureDoi="http://doi.org/10.5281/zenodo.10491074" httpUri="https://zenodo.org/record/10491074/files/figure.png" pageId="5" pageNumber="131">Fig. 3</figureCitation>
|
||
). The conformer carrying the pseudoequatorially oriented H
|
||
<subScript id="178434DFDF133F41A7B83AE4FD2DFA13" attach="right" box="[666,675,1473,1485]" fontSize="5" pageId="5" pageNumber="131">3</subScript>
|
||
-14 group was largely favored for all compounds. On the other hand, the conjugated diene system conferred a high rigidity to the central seven-membered ring on which the equatorial orientation of the H
|
||
<subScript id="178434DFDF133F41A5A03914FF05F9E3" attach="right" box="[130,139,1585,1597]" fontSize="5" pageId="5" pageNumber="131">3</subScript>
|
||
-12 group was highly preferred. Subsequently, the
|
||
<superScript id="7C759BD2DF133F41A7903901FD4AF9EE" attach="right" box="[690,708,1572,1584]" fontSize="5" pageId="5" pageNumber="131">13</superScript>
|
||
C
|
||
<collectionCode id="ED11AE5FDF133F41A7FF390DFC81F9E5" box="[733,783,1576,1595]" country="Netherlands" httpUri="http://grbio.org/cool/jyde-k516" name="Natuurhistorisch Museum" pageId="5" pageNumber="131">NMR</collectionCode>
|
||
chemical shifts were calculated for the most populated conformer of each structure, namely for
|
||
<emphasis id="B974EA88DF133F41A48D397AFE5BF9AC" bold="true" box="[431,469,1631,1650]" pageId="5" pageNumber="131">13a</emphasis>
|
||
,
|
||
<emphasis id="B974EA88DF133F41A4C6397AFD96F9AC" bold="true" box="[484,536,1629,1652]" pageId="5" pageNumber="131">14oia</emphasis>
|
||
,
|
||
<emphasis id="B974EA88DF133F41A705397AFDD9F9AC" bold="true" box="[551,599,1631,1650]" pageId="5" pageNumber="131">14ƥa</emphasis>
|
||
,
|
||
<emphasis id="B974EA88DF133F41A745397AFD14F9AC" bold="true" box="[615,666,1629,1652]" pageId="5" pageNumber="131">15oia</emphasis>
|
||
, and
|
||
<emphasis id="B974EA88DF133F41A7F8397AFC84F9AC" bold="true" box="[730,778,1631,1650]" pageId="5" pageNumber="131">15ƥa</emphasis>
|
||
, using two-step spin–spin coupling calculation (
|
||
<bibRefCitation id="EF914B6BDF133F41A77B3959FC89F950" author="Deng, W. & Cheeseman, J. R. & Frisch, M. J." box="[601,775,1659,1679]" pageId="5" pageNumber="131" pagination="1028 - 1037" refId="ref10622" refString="Deng, W., Cheeseman, J. R., Frisch, M. J., 2006. Calculation of nuclear spin - spin coupling constants of molecules with first and second row atoms in study of basis set dependence. J. Chem. Theory and Comput. 2, 1028 - 1037." type="journal article" year="2006">Deng et al., 2006</bibRefCitation>
|
||
) and considering CD
|
||
<subScript id="178434DFDF133F41A4193985FECAF972" attach="both" box="[315,324,1696,1708]" fontSize="5" pageId="5" pageNumber="131">2</subScript>
|
||
Cl
|
||
<subScript id="178434DFDF133F41A47A3985FEEFF972" attach="left" box="[344,353,1696,1708]" fontSize="5" pageId="5" pageNumber="131">2</subScript>
|
||
as the solvent and TMS as the reference standard.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF133F41A5B339EAFC81F803" blockId="5.[113,783,1213,2013]" pageId="5" pageNumber="131">
|
||
The computed carbon resonances for the modeled structures are reported in
|
||
<tableCitation id="C6820321DF133F41A43639CEFEEEF920" box="[276,352,1771,1790]" captionStart="Table 1" captionStartId="2.[87,131,183,197]" captionText="Table 1 Experimental (75.47 MHz, CD Cl) 13C NMR resonances (δ) for compound 7a and russulanobilines A–C, and calculated 13C NMR resonances (δ) for structures 13a, 14oia, 14ƥa, 2 2 C C 15oia, and 15ƥa." pageId="5" pageNumber="131">Table 1</tableCitation>
|
||
, compared with the experimental data of russulanobilines B and C. The good correspondence between the experimentally determined
|
||
<superScript id="7C759BD2DF133F41A4A8383AFE13F8F5" attach="right" box="[394,413,1823,1835]" fontSize="5" pageId="5" pageNumber="131">13</superScript>
|
||
C
|
||
<collectionCode id="ED11AE5FDF133F41A48D3806FE6FF8E8" box="[431,481,1827,1846]" country="Netherlands" httpUri="http://grbio.org/cool/jyde-k516" name="Natuurhistorisch Museum" pageId="5" pageNumber="131">NMR</collectionCode>
|
||
resonances of russulanobiline B and the calculated chemical shifts for structure
|
||
<emphasis id="B974EA88DF133F41A748381BFD0DF88F" bold="true" box="[618,643,1854,1873]" pageId="5" pageNumber="131">13</emphasis>
|
||
validated the method. Of particular importance was the close similarity between the experimental and computed chemical shifts of the conjugated diene system C-6/C-7/C-8/C-9. On the other hand, the comparison of the experimental resonances of the C-6/C-7/C-8/C-9 diene unit in russulanobiline C and the calculated chemical shifts of the same
|
||
</paragraph>
|
||
</subSection>
|
||
<subSection id="E28F2F71DF133F42A61D3BA1FD23FEE7" lastPageId="6" lastPageNumber="132" pageId="5" pageNumber="131" type="multiple">
|
||
<paragraph id="8BBF369ADF133F41A61D3BA1FAB0FB46" blockId="5.[831,1342,1156,1176]" box="[831,1342,1156,1176]" pageId="5" pageNumber="131">
|
||
<heading id="D0F781F6DF133F41A61D3BA1FAB0FB46" box="[831,1342,1156,1176]" fontSize="36" level="2" pageId="5" pageNumber="131" reason="3">
|
||
<emphasis id="B974EA88DF133F41A61D3BA1FAB0FB46" box="[831,1342,1156,1176]" italics="true" pageId="5" pageNumber="131">2.4. Absolute configuration of isolated sesquiterpenes</emphasis>
|
||
</heading>
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF133F42A67C3B98FD23FEE7" blockId="5.[831,1501,1213,2013]" lastBlockId="6.[87,757,181,313]" lastPageId="6" lastPageNumber="132" pageId="5" pageNumber="131">
|
||
The absolute configuration of the
|
||
<taxonomicName id="4C004D19DF133F41A1E13B98FAB3FB0E" authorityName="Lotsy" authorityYear="1907" box="[1219,1341,1213,1232]" class="Agaricomycetes" family="Russulaceae" kingdom="Fungi" order="Russulales" pageId="5" pageNumber="131" phylum="Basidiomycota" rank="family">Russulaceae</taxonomicName>
|
||
sesquiterpenes derived from velutinal esters of
|
||
<typeStatus id="54BB8838DF133F41A1A33BFCFB20FB32" box="[1153,1198,1241,1260]" pageId="5" pageNumber="131">type</typeStatus>
|
||
<emphasis id="B974EA88DF133F41A1963BFCFB4FFB32" bold="true" box="[1204,1217,1241,1260]" pageId="5" pageNumber="131">1</emphasis>
|
||
is based on that of (+)-isovelleral
|
||
<emphasis id="B974EA88DF133F41A6A83BD0FC2DFAD6" bold="true" box="[906,931,1269,1288]" pageId="5" pageNumber="131">16</emphasis>
|
||
, which was established by an enantioselective total synthesis (
|
||
<bibRefCitation id="EF914B6BDF133F41A6923A34FB03FAFA" author="Bergman, R. & Hansson, T. & Sterner, O. & Wickberg, B." box="[944,1165,1296,1316]" pageId="5" pageNumber="131" pagination="865 - 867" refId="ref9995" refString="Bergman, R., Hansson, T., Sterner, O., Wickberg, B., 1990. A total synthesis of (+) - isovelleral. The absolute configuration of the Russulaceae sesquiterpenes. J. Chem. Soc., Chem. Commun., 865 - 867." type="book chapter" year="1990">Bergman et al., 1990</bibRefCitation>
|
||
). In fact, stereochemically controlled intercorrelations (
|
||
<bibRefCitation id="EF914B6BDF133F41A1643A09FAEAFAE1" author="Vidari, G. & Vita-Finzi, P." box="[1094,1380,1324,1343]" pageId="5" pageNumber="131" pagination="152 - 206" refId="ref11924" refString="Vidari, G., Vita-Finzi, P., 1995. Sesquiterpenes and other secondary metabolites of the genus Lactarius (Basidiomycetes): chemistry and biological activity. In: Atta-ur-Rahman (Ed.), Studies in natural product chemistry structure and chemistry, vol. 17. Elsevier, Amsterdam, pp. 152 - 206." type="book chapter" year="1995">Vidari and Vita-Finzi, 1995</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF133F41A0513A09FC6DFA85" author="Daniewski, W. M. & Vidari, G." pageId="5" pageNumber="131" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
) and correlations also with (+)-isovelleral
|
||
<emphasis id="B974EA88DF133F41A0AA3A6DFA2FFA85" bold="true" box="[1416,1441,1352,1371]" pageId="5" pageNumber="131">16</emphasis>
|
||
demonstrated that the marasmane and lactarane sesquiterpenes formed in
|
||
<taxonomicName id="4C004D19DF133F41A68D3A5AFB88FA4D" box="[943,1030,1407,1427]" class="Agaricomycetes" family="Russulaceae" genus="Lactarius" kingdom="Fungi" order="Russulales" pageId="5" pageNumber="131" phylum="Basidiomycota" rank="genus">
|
||
<emphasis id="B974EA88DF133F41A68D3A5AFB88FA4D" box="[943,1030,1407,1427]" italics="true" pageId="5" pageNumber="131">Lactarius</emphasis>
|
||
</taxonomicName>
|
||
and
|
||
<taxonomicName id="4C004D19DF133F41A11D3A5AFB06FA4D" box="[1087,1160,1407,1427]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="5" pageNumber="131" phylum="Basidiomycota" rank="genus">
|
||
<emphasis id="B974EA88DF133F41A11D3A5AFB06FA4D" box="[1087,1160,1407,1427]" italics="true" pageId="5" pageNumber="131">Russula</emphasis>
|
||
</taxonomicName>
|
||
damaged fruiting bodies belong to the same enantiomeric series as that of their biosynthetic precursor
|
||
<emphasis id="B974EA88DF133F41A68B3A9DFC38FA15" bold="true" box="[937,950,1464,1483]" pageId="5" pageNumber="131">1</emphasis>
|
||
. Plausible mechanisms have also been suggested to explain the characteristic stereochemistry of different sesquiterpenes enzymatically derived from velutinal esters in injured
|
||
<taxonomicName id="4C004D19DF133F41A08D3AD5FC1AF9C1" authorityName="Lotsy" authorityYear="1907" class="Agaricomycetes" family="Russulaceae" kingdom="Fungi" order="Russulales" pageId="5" pageNumber="131" phylum="Basidiomycota" rank="family">Russulaceae</taxonomicName>
|
||
fruiting bodies (
|
||
<bibRefCitation id="EF914B6BDF133F41A1603929FAB4F9C1" author="De Bernardi, M. & Garlaschelli, L. & Toma, L. & Vidari, G. & Vita-Finzi, P." box="[1090,1338,1548,1567]" pageId="5" pageNumber="131" pagination="1489 - 1504" refId="ref10514" refString="De Bernardi, M., Garlaschelli, L., Toma, L., Vidari, G., Vita-Finzi, P., 1993. The chemical basis of hot-tasting and yellowing of the mushrooms Lactarius chrysorrheus and L. scrobiculatus. Tetrahedron 49, 1489 - 1504." type="journal article" year="1993">De Bernardi et al., 1993</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF133F41A0643929FCFCF9E5" author="Hansson, T. & Pang, Z. & Sterner, O." pageId="5" pageNumber="131" pagination="403 - 405" refId="ref11336" refString="Hansson, T., Pang, Z., Sterner, O., 1993. The conversion of [12 - 2 H 3] - labelled velutinal in injured fruit bodies of Lactarius vellereus. Further insight into the biosynthesis of the Russulaceae sesquiterpenes. Acta Chem. Scand. 47, 403 - 405." type="journal article" year="1993">Hansson et al., 1993</bibRefCitation>
|
||
). The co-occurrence of new sesquiterpenes
|
||
<emphasis id="B974EA88DF133F41A01A3902FAF9F9E4" bold="true" box="[1336,1399,1575,1595]" pageId="5" pageNumber="131">12–14</emphasis>
|
||
with stereodefined compounds
|
||
<emphasis id="B974EA88DF133F41A10C3966FBEEF988" bold="true" box="[1070,1120,1603,1623]" pageId="5" pageNumber="131">3–10</emphasis>
|
||
, and their common origin from ester
|
||
<quantity id="4CF89B7FDF133F41A61D397AFCEBF9AC" box="[831,869,1631,1650]" metricMagnitude="-2" metricUnit="m" metricValue="2.54" pageId="5" pageNumber="131" unit="in" value="1.0">
|
||
<emphasis id="B974EA88DF133F41A61D397AFCC2F9AC" bold="true" box="[831,844,1631,1650]" pageId="5" pageNumber="131">1</emphasis>
|
||
in
|
||
</quantity>
|
||
injured fruiting bodies of
|
||
<taxonomicName id="4C004D19DF133F41A148397BFB4FF9AC" box="[1130,1217,1630,1650]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="5" pageNumber="131" phylum="Basidiomycota" rank="species" species="nobilis">
|
||
<emphasis id="B974EA88DF133F41A148397BFB4FF9AC" box="[1130,1217,1630,1650]" italics="true" pageId="5" pageNumber="131">R. nobilis</emphasis>
|
||
</taxonomicName>
|
||
, indicated the absolute configuration shown in the formulae. This homochiral stereochemistry of compounds
|
||
<emphasis id="B974EA88DF133F41A6F439B2FB86F974" bold="true" box="[982,1032,1687,1707]" pageId="5" pageNumber="131">1–14</emphasis>
|
||
was confirmed by the conversion of 5-lactaranolide
|
||
<emphasis id="B974EA88DF133F41A6B13996FC25F918" bold="true" box="[915,939,1715,1734]" pageId="5" pageNumber="131">7a</emphasis>
|
||
to conjugated anhydrolactarorufin
|
||
<taxonomicName id="4C004D19DF133F41A0033996FA0FF918" box="[1313,1409,1715,1734]" class="Agaricomycetes" family="Amanitaceae" genus="Amanita" kingdom="Fungi" order="Agaricales" pageId="5" pageNumber="131" phylum="Basidiomycota" rank="species" species="acetate">A acetate</taxonomicName>
|
||
(
|
||
<emphasis id="B974EA88DF133F41A0B63991FA2BF918" box="[1428,1445,1716,1734]" italics="true" pageId="5" pageNumber="131">—</emphasis>
|
||
)
|
||
<emphasis id="B974EA88DF133F41A08E3991FA33F918" box="[1452,1469,1716,1734]" italics="true" pageId="5" pageNumber="131">—</emphasis>
|
||
<emphasis id="B974EA88DF133F41A09F3996FA56F918" bold="true" box="[1469,1496,1715,1734]" pageId="5" pageNumber="131">7b</emphasis>
|
||
, identical with the compound obtained from (+)-lactarorufin A
|
||
<emphasis id="B974EA88DF133F41A0ED39EAFA52F93C" bold="true" box="[1487,1500,1743,1762]" pageId="5" pageNumber="131">8</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF133F41A66539CEFBA3F920" author="Daniewski, W. M. & Kocor, M. & Krol, J." box="[839,1069,1771,1790]" pageId="5" pageNumber="131" pagination="2095 - 2100" refId="ref10238" refString="Daniewski, W. M., Kocor, M., Krol, J., 1976. Constituents of higher fungi. Part VII. Lactarorufin N and revised structures of lactarorufins. Roczniki Chem. 50, 2095 - 2100." type="journal article" year="1976">Daniewski et al., 1976</bibRefCitation>
|
||
). Moreover, the absolute configuration of russulanobiline B (
|
||
<emphasis id="B974EA88DF133F41A6D93822FB9AF8C4" bold="true" box="[1019,1044,1799,1818]" pageId="5" pageNumber="131">13</emphasis>
|
||
) was further supported by CD measurement. In fact, Gawronski et al. have discovered a simple CD method for assigning the absolute configuration to an allylic alcohol in a ring fused to a 2(5
|
||
<emphasis id="B974EA88DF133F41A6EC387CFC50F8B3" box="[974,990,1881,1901]" italics="true" pageId="5" pageNumber="131">H</emphasis>
|
||
)-furanone ring (
|
||
<bibRefCitation id="EF914B6BDF133F41A1AB387FFAFEF8B3" author="Gawronski, J. K. & van Oeveren, A. & van der Deen, H. & Leung, C. W. & Feringa, B. L." box="[1161,1392,1882,1902]" pageId="5" pageNumber="131" pagination="1513 - 1515" refId="ref11210" refString="Gawronski, J. K., van Oeveren, A., van der Deen, H., Leung, C. W., Feringa, B. L., 1996. Simple circular dichroic method for the determination of absolute configuration of 5 - substituted 2 (5 H) - furanones. J. Org. Chem. 61, 1513 - 1515." type="journal article" year="1996">Gawronski et al., 1996</bibRefCitation>
|
||
). The proposed helicity rule was also demonstrated by the Cotton effects of opposite signs determined for the diastereomeric (+)-lactarorufin A
|
||
<emphasis id="B974EA88DF133F41A656388BFC0FF81F" bold="true" box="[884,897,1966,1985]" pageId="5" pageNumber="131">8</emphasis>
|
||
and (
|
||
<emphasis id="B974EA88DF133F41A699388AFC42F81F" box="[955,972,1967,1985]" italics="true" pageId="5" pageNumber="131">—</emphasis>
|
||
)-8-
|
||
<emphasis id="B974EA88DF133F41A6D13888FB9EF81F" box="[1011,1040,1965,1985]" italics="true" pageId="5" pageNumber="131">epi</emphasis>
|
||
-lactarorufin A (
|
||
<emphasis id="B974EA88DF133F41A193388BFB44F81F" bold="true" box="[1201,1226,1966,1985]" pageId="5" pageNumber="131">17</emphasis>
|
||
) which have opposite configuration at C-8 (
|
||
<bibRefCitation id="EF914B6BDF133F41A6DB38EFFA9CF803" author="Daniewski, W. M. & Kocor, M." box="[1017,1298,1994,2013]" pageId="5" pageNumber="131" pagination="553 - 561" refId="ref10191" refString="Daniewski, W. M., Kocor, M., 1971. Constituents of higher fungi. II. Structure of lactarorufin A .. Bull. Acad. Polon. Sci., Ser. Sci. Chim. 19, 553 - 561." type="journal article" year="1971">Daniewski and Kocor, 1971</bibRefCitation>
|
||
). Russulanobiline B (
|
||
<emphasis id="B974EA88DF103F42A57D3F93FFF6FF17" bold="true" box="[95,120,182,201]" pageId="6" pageNumber="132">13</emphasis>
|
||
), similarly to (
|
||
<emphasis id="B974EA88DF103F42A43B3F92FEA4FF17" box="[281,298,183,201]" italics="true" pageId="6" pageNumber="132">—</emphasis>
|
||
)-8-
|
||
<emphasis id="B974EA88DF103F42A4723F90FEE3FF17" box="[336,365,181,201]" italics="true" pageId="6" pageNumber="132">epi</emphasis>
|
||
-lactarorufin A (
|
||
<emphasis id="B974EA88DF103F42A7343F93FDA1FF17" bold="true" box="[534,559,182,201]" pageId="6" pageNumber="132">17</emphasis>
|
||
), showed negative sign of the n
|
||
<emphasis id="B974EA88DF103F42A5C13FF6FF77FF3B" box="[227,249,211,229]" italics="true" pageId="6" pageNumber="132">+</emphasis>
|
||
π
|
||
<emphasis id="B974EA88DF103F42A42E3FEAFE9AFF07" bold="true" box="[268,276,207,217]" italics="true" pageId="6" pageNumber="132">
|
||
<superScript id="7C759BD2DF103F42A42E3FEAFE9AFF07" attach="right" box="[268,276,207,217]" fontSize="5" pageId="6" pageNumber="132">⁄</superScript>
|
||
</emphasis>
|
||
transition Cotton effect at
|
||
<quantity id="4CF89B7FDF103F42A7163FF7FD0CFF38" box="[564,642,210,230]" metricMagnitude="-7" metricUnit="m" metricValue="2.55" pageId="6" pageNumber="132" unit="nm" value="255.0">255 nm</quantity>
|
||
. Therefore, on the basis of the helicity rule for the HO–C–C
|
||
<emphasis id="B974EA88DF103F42A70A3FCAFDB4FEDE" bold="true" box="[552,570,239,256]" pageId="6" pageNumber="132">@</emphasis>
|
||
C–CO bond system (
|
||
<bibRefCitation id="EF914B6BDF103F42A57D3E2FFECFFEC3" author="Gawronski, J. K. & van Oeveren, A. & van der Deen, H. & Leung, C. W. & Feringa, B. L." box="[95,321,266,285]" pageId="6" pageNumber="132" pagination="1513 - 1515" refId="ref11210" refString="Gawronski, J. K., van Oeveren, A., van der Deen, H., Leung, C. W., Feringa, B. L., 1996. Simple circular dichroic method for the determination of absolute configuration of 5 - substituted 2 (5 H) - furanones. J. Org. Chem. 61, 1513 - 1515." type="journal article" year="1996">Gawronski et al., 1996</bibRefCitation>
|
||
), the (
|
||
<emphasis id="B974EA88DF103F42A4A13E2CFE1EFEC3" box="[387,400,265,285]" italics="true" pageId="6" pageNumber="132">
|
||
<collectionCode id="ED11AE5FDF103F42A4A13E2CFE1EFEC3" box="[387,400,265,285]" country="Chile" name="Departamento de Geologia, Universidad de Chile" pageId="6" pageNumber="132">R</collectionCode>
|
||
</emphasis>
|
||
)-configuration at C-8 of compound
|
||
<emphasis id="B974EA88DF103F42A5753E03FFFEFEE7" bold="true" box="[87,112,294,313]" pageId="6" pageNumber="132">13</emphasis>
|
||
was confirmed, and hence its absolute stereochemistry.
|
||
</paragraph>
|
||
</subSection>
|
||
</subSubSection>
|
||
<subSection id="E28F2F71DF103F42A5753E5CFCDEFCF1" pageId="6" pageNumber="132" type="multiple">
|
||
<subSubSection id="C31A6511DF103F42A5753E5CFCDEFCF1" pageId="6" pageNumber="132" type="discussion">
|
||
<paragraph id="8BBF369ADF103F42A5753E5CFF7EFE52" blockId="6.[87,240,377,396]" box="[87,240,377,396]" pageId="6" pageNumber="132">
|
||
<heading id="D0F781F6DF103F42A5753E5CFF7EFE52" bold="true" box="[87,240,377,396]" fontSize="36" level="1" pageId="6" pageNumber="132" reason="1">
|
||
<emphasis id="B974EA88DF103F42A5753E5CFF7EFE52" bold="true" box="[87,240,377,396]" pageId="6" pageNumber="132">3. Conclusions</emphasis>
|
||
</heading>
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF103F42A5543E94FD26FAD7" blockId="6.[87,758,432,2015]" pageId="6" pageNumber="132">
|
||
Our findings on the contents of
|
||
<taxonomicName id="4C004D19DF103F42A4923E95FD8BFE1A" box="[432,517,432,452]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="6" pageNumber="132" phylum="Basidiomycota" rank="species" species="nobilis">
|
||
<emphasis id="B974EA88DF103F42A4923E95FD8BFE1A" box="[432,517,432,452]" italics="true" pageId="6" pageNumber="132">R. nobilis</emphasis>
|
||
</taxonomicName>
|
||
confirm that there is no clear-cut chemical separation between the majority of
|
||
<taxonomicName id="4C004D19DF103F42A7A23EE9FD47FE3E" box="[640,713,460,480]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="6" pageNumber="132" phylum="Basidiomycota" rank="genus">
|
||
<emphasis id="B974EA88DF103F42A7A23EE9FD47FE3E" box="[640,713,460,480]" italics="true" pageId="6" pageNumber="132">Russula</emphasis>
|
||
</taxonomicName>
|
||
and
|
||
<taxonomicName id="4C004D19DF103F42A5753ECDFF72FE22" box="[87,252,488,508]" pageId="6" pageNumber="132">
|
||
<emphasis id="B974EA88DF103F42A5753ECDFF20FE22" box="[87,174,488,508]" italics="true" pageId="6" pageNumber="132">Lactarius</emphasis>
|
||
species
|
||
</taxonomicName>
|
||
as far as the content of sesquiterpene metabolites in undamaged fruiting bodies is concerned. In fact, intact fruiting bodies of most bitter or pungent
|
||
<taxonomicName id="4C004D19DF103F42A48D3D04FDA7FDEA" authorityName="Lotsy" authorityYear="1907" box="[431,553,545,564]" class="Agaricomycetes" family="Russulaceae" kingdom="Fungi" order="Russulales" pageId="6" pageNumber="132" phylum="Basidiomycota" rank="family">Russulaceae</taxonomicName>
|
||
species contain the marasmane sesquiterpene velutinal in the form of tasteless fatty acid esters, such as
|
||
<emphasis id="B974EA88DF103F42A4003D7CFEA1FDB2" bold="true" box="[290,303,601,620]" pageId="6" pageNumber="132">1</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF103F42A41C3D7CFDDDFDB2" author="Vidari, G. & Vita-Finzi, P." box="[318,595,601,620]" pageId="6" pageNumber="132" pagination="152 - 206" refId="ref11924" refString="Vidari, G., Vita-Finzi, P., 1995. Sesquiterpenes and other secondary metabolites of the genus Lactarius (Basidiomycetes): chemistry and biological activity. In: Atta-ur-Rahman (Ed.), Studies in natural product chemistry structure and chemistry, vol. 17. Elsevier, Amsterdam, pp. 152 - 206." type="book chapter" year="1995">Vidari and Vita-Finzi, 1995</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF103F42A77D3D7CFF59FD56" author="Daniewski, W. M. & Vidari, G." pageId="6" pageNumber="132" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF103F42A5C03D50FE33FD56" author="Clericuzio, M. & Gilardoni, G. & Malagon, O. & Vidari, G. & Vita-Finzi, P." box="[226,445,629,648]" pageId="6" pageNumber="132" pagination="951 - 974" refId="ref10051" refString="Clericuzio, M., Gilardoni, G., Malagon, O., Vidari, G., Vita-Finzi, P., 2008. Sesquiterpenes of Lactarius and Russula (mushrooms): an update. Nat. Prod. Commun. 3, 951 - 974." type="journal article" year="2008">Clericuzio et al., 2008</bibRefCitation>
|
||
). However, the pattern of sesquiterpenes formed upon an injury to fruiting bodies is usually dramatically different from species to species (
|
||
<bibRefCitation id="EF914B6BDF103F42A7693D89FF45FD05" author="Vidari, G. & Vita-Finzi, P." pageId="6" pageNumber="132" pagination="152 - 206" refId="ref11924" refString="Vidari, G., Vita-Finzi, P., 1995. Sesquiterpenes and other secondary metabolites of the genus Lactarius (Basidiomycetes): chemistry and biological activity. In: Atta-ur-Rahman (Ed.), Studies in natural product chemistry structure and chemistry, vol. 17. Elsevier, Amsterdam, pp. 152 - 206." type="book chapter" year="1995">Vidari and Vita-Finzi, 1995</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF103F42A5FB3DEDFE75FD05" author="Daniewski, W. M. & Vidari, G." box="[217,507,712,731]" pageId="6" pageNumber="132" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF103F42A7253DEDFD69FD05" author="Clericuzio, M. & Gilardoni, G. & Malagon, O. & Vidari, G. & Vita-Finzi, P." box="[519,743,712,732]" pageId="6" pageNumber="132" pagination="951 - 974" refId="ref10051" refString="Clericuzio, M., Gilardoni, G., Malagon, O., Vidari, G., Vita-Finzi, P., 2008. Sesquiterpenes of Lactarius and Russula (mushrooms): an update. Nat. Prod. Commun. 3, 951 - 974." type="journal article" year="2008">Clericuzio et al., 2008</bibRefCitation>
|
||
), and such characteristic differences are chemotaxonomically important. A further example is given by the compounds isolated from
|
||
<taxonomicName id="4C004D19DF103F42A5B63C3EFF7FFCF1" box="[148,241,795,815]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="6" pageNumber="132" phylum="Basidiomycota" rank="species" species="nobilis">
|
||
<emphasis id="B974EA88DF103F42A5B63C3EFF7FFCF1" box="[148,241,795,815]" italics="true" pageId="6" pageNumber="132">R. nobilis</emphasis>
|
||
</taxonomicName>
|
||
, which nicely characterize this mushroom with respect to the other
|
||
<taxonomicName id="4C004D19DF103F42A40A3C12FE4EFC95" box="[296,448,823,843]" pageId="6" pageNumber="132">
|
||
<emphasis id="B974EA88DF103F42A40A3C12FEFFFC95" box="[296,369,823,843]" italics="true" pageId="6" pageNumber="132">Russula</emphasis>
|
||
species
|
||
</taxonomicName>
|
||
investigated so far (
|
||
<bibRefCitation id="EF914B6BDF103F42A7B33C1DFF40FCB9" author="Clericuzio, M. & Gilardoni, G. & Malagon, O. & Vidari, G. & Vita-Finzi, P." pageId="6" pageNumber="132" pagination="951 - 974" refId="ref10051" refString="Clericuzio, M., Gilardoni, G., Malagon, O., Vidari, G., Vita-Finzi, P., 2008. Sesquiterpenes of Lactarius and Russula (mushrooms): an update. Nat. Prod. Commun. 3, 951 - 974." type="journal article" year="2008">Clericuzio et al., 2008</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF103F42A5F93C71FE31FCB9" author="Clericuzio, M. & Cassino, C. & Corana, F. & Vidari, G." box="[219,447,852,871]" pageId="6" pageNumber="132" pagination="154 - 159" refId="ref10102" refString="Clericuzio, M., Cassino, C., Corana, F., Vidari, G., 2012. Terpenoids from Russula Lepida and R. amarissima (Basidiomycota, Russulaceae). Phytochem 84, 154 - 159." type="journal article" year="2012">Clericuzio et al., 2012</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF103F42A4E93C71FD05FCB9" author="Yaoita, Y. & Hirao, M. & Kikuchi, M. & Machida, K." box="[459,651,852,871]" pageId="6" pageNumber="132" pagination="1133 - 1135" refId="ref11985" refString="Yaoita, Y., Hirao, M., Kikuchi, M., Machida, K., 2012. Three new lactarane sesquiterpenoids from the mushroom Russula sanguinea. Nat. Prod. Commun. 7, 1133 - 1135." type="journal article" year="2012">Yaoita et al., 2012</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF103F42A7B53C71FF4BFC5D" author="Gilardoni, G. & Malagon, O. & Tosi, S. & Clericuzio, M. & Vidari, G." pageId="6" pageNumber="132" pagination="319 - 322" refId="ref11280" refString="Gilardoni, G., Malagon, O., Tosi, S., Clericuzio, M., Vidari, G., 2014. Lactarane Sesquiterpenes from the European Mushrooms Lactarius aurantiacus, L. subdulcis, and Russula sanguinaria. Nat. Prod. Commun. 9, 319 - 322." type="journal article" year="2014">Gilardoni et al., 2014</bibRefCitation>
|
||
). This diversity very likely reflects the existence of various enzymatic systems at work in each mushroom species, which control multi-step rearrangements of the original pentacyclic velutinal skeleton into other structures and modulate the oxidation state at specific carbon positions. Thus, lactaronobilines
|
||
<emphasis id="B974EA88DF103F42A7973CFAFD7AFC2C" bold="true" box="[693,756,991,1011]" pageId="6" pageNumber="132">12–14</emphasis>
|
||
likely derive from oxidations of velleral (
|
||
<emphasis id="B974EA88DF103F42A4D53CD9FD86FBD0" box="[503,520,1020,1038]" italics="true" pageId="6" pageNumber="132">—</emphasis>
|
||
)
|
||
<emphasis id="B974EA88DF103F42A7323CD9FDAFFBD0" box="[528,545,1020,1038]" italics="true" pageId="6" pageNumber="132">—</emphasis>
|
||
<emphasis id="B974EA88DF103F42A7023CDEFDA3FBD0" bold="true" box="[544,557,1019,1038]" pageId="6" pageNumber="132">3</emphasis>
|
||
which, in damaged fruiting bodies of
|
||
<taxonomicName id="4C004D19DF103F42A42D3B33FEE9FBF4" box="[271,359,1046,1066]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="6" pageNumber="132" phylum="Basidiomycota" rank="species" species="nobilis">
|
||
<emphasis id="B974EA88DF103F42A42D3B33FEE9FBF4" box="[271,359,1046,1066]" italics="true" pageId="6" pageNumber="132">R. nobilis</emphasis>
|
||
</taxonomicName>
|
||
, is enzymatically formed in a few seconds from velutinal esters of
|
||
<typeStatus id="54BB8838DF103F42A4583B16FE29FB98" box="[378,423,1075,1094]" pageId="6" pageNumber="132">type</typeStatus>
|
||
<emphasis id="B974EA88DF103F42A48E3B16FE37FB98" bold="true" box="[428,441,1075,1094]" pageId="6" pageNumber="132">1</emphasis>
|
||
. Indeed, regiospecific oxidation of the two carbonyl groups in velleral
|
||
<emphasis id="B974EA88DF103F42A4FB3B6AFE68FBBC" bold="true" box="[473,486,1103,1122]" pageId="6" pageNumber="132">3</emphasis>
|
||
may lead to the
|
||
<specimenCount id="9D06FD13DF103F42A7B33B6AFD7BFBBC" box="[657,757,1103,1122]" count="2" pageId="6" pageNumber="132" type="generic" typeStatus="types">two types</specimenCount>
|
||
of lactarane lactones found in
|
||
<taxonomicName id="4C004D19DF103F42A4AB3B4FFE6EFBA0" box="[393,480,1130,1150]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="6" pageNumber="132" phylum="Basidiomycota" rank="species" species="nobilis">
|
||
<emphasis id="B974EA88DF103F42A4AB3B4FFE6EFBA0" box="[393,480,1130,1150]" italics="true" pageId="6" pageNumber="132">R. nobilis</emphasis>
|
||
</taxonomicName>
|
||
, having the carbonyl group either at C-5 (5-lactaranolides), such as in compounds
|
||
<emphasis id="B974EA88DF103F42A7563BA3FD29FB47" bold="true" box="[628,679,1158,1178]" pageId="6" pageNumber="132">6–12</emphasis>
|
||
or at C-13 (13-lactaranolides), such as in
|
||
<emphasis id="B974EA88DF103F42A4FC3B87FE79FB6B" bold="true" box="[478,503,1186,1205]" pageId="6" pageNumber="132">13</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF103F42A71C3B87FDD9FB6B" bold="true" box="[574,599,1186,1205]" pageId="6" pageNumber="132">14</emphasis>
|
||
. Alternatively, hydroxylactones
|
||
<emphasis id="B974EA88DF103F42A4243B9BFE91FB0F" bold="true" box="[262,287,1214,1233]" pageId="6" pageNumber="132">13</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF103F42A4753B9BFEFEFB0F" bold="true" box="[343,368,1214,1233]" pageId="6" pageNumber="132">14</emphasis>
|
||
may derive from regiospecific oxidation of furans, such as furandiol (+)
|
||
<emphasis id="B974EA88DF103F42A4C23BFEFE7FFB33" box="[480,497,1243,1261]" italics="true" pageId="6" pageNumber="132">—</emphasis>
|
||
<emphasis id="B974EA88DF103F42A4D33BFFFE70FB33" bold="true" box="[497,510,1242,1261]" pageId="6" pageNumber="132">5</emphasis>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF103F42A7303BFFFF03FAD7" author="Vidari, G. & Vita-Finzi, P." pageId="6" pageNumber="132" pagination="152 - 206" refId="ref11924" refString="Vidari, G., Vita-Finzi, P., 1995. Sesquiterpenes and other secondary metabolites of the genus Lactarius (Basidiomycetes): chemistry and biological activity. In: Atta-ur-Rahman (Ed.), Studies in natural product chemistry structure and chemistry, vol. 17. Elsevier, Amsterdam, pp. 152 - 206." type="book chapter" year="1995">Vidari and Vita-Finzi, 1995</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF103F42A5BB3BD3FE3BFAD7" author="Daniewski, W. M. & Vidari, G." box="[153,437,1270,1289]" pageId="6" pageNumber="132" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF103F42A4E23BD3FD15FAD7" author="Clericuzio, M. & Gilardoni, G. & Malagon, O. & Vidari, G. & Vita-Finzi, P." box="[448,667,1270,1290]" pageId="6" pageNumber="132" pagination="951 - 974" refId="ref10051" refString="Clericuzio, M., Gilardoni, G., Malagon, O., Vidari, G., Vita-Finzi, P., 2008. Sesquiterpenes of Lactarius and Russula (mushrooms): an update. Nat. Prod. Commun. 3, 951 - 974." type="journal article" year="2008">Clericuzio et al., 2008</bibRefCitation>
|
||
).
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF103F42A5543A37FD78FA83" blockId="6.[87,758,432,2015]" pageId="6" pageNumber="132">
|
||
5-Lactaranolides are much more widespread than 13-lactaranolides in
|
||
<taxonomicName id="4C004D19DF103F42A5883A0BFEA8FA9F" authorityName="Lotsy" authorityYear="1907" box="[170,294,1326,1345]" class="Agaricomycetes" family="Russulaceae" kingdom="Fungi" order="Russulales" pageId="6" pageNumber="132" phylum="Basidiomycota" rank="family">Russulaceae</taxonomicName>
|
||
. Actually, compounds
|
||
<emphasis id="B974EA88DF103F42A72F3A0BFDA8FA9F" bold="true" box="[525,550,1326,1345]" pageId="6" pageNumber="132">13</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF103F42A7793A0BFDFAFA9F" bold="true" box="[603,628,1326,1345]" pageId="6" pageNumber="132">14</emphasis>
|
||
are the first examples of 13-lactaranolides isolated from
|
||
<taxonomicName id="4C004D19DF103F42A7323A6CFDD7FA83" box="[528,601,1353,1373]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="6" pageNumber="132" phylum="Basidiomycota" rank="genus">
|
||
<emphasis id="B974EA88DF103F42A7323A6CFDD7FA83" box="[528,601,1353,1373]" italics="true" pageId="6" pageNumber="132">Russula</emphasis>
|
||
</taxonomicName>
|
||
fruiting bodies.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF103F42A5543A43FE3AF916" blockId="6.[87,758,432,2015]" pageId="6" pageNumber="132">
|
||
The pungent velleral
|
||
<emphasis id="B974EA88DF103F42A46F3A43FED4FAA7" bold="true" box="[333,346,1382,1401]" pageId="6" pageNumber="132">3</emphasis>
|
||
and the bitter lactarorufins
|
||
<emphasis id="B974EA88DF103F42A7553A43FD01FAA7" bold="true" box="[631,655,1382,1401]" pageId="6" pageNumber="132">7a</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF103F42A7E03A43FD41FAA7" bold="true" box="[706,719,1382,1401]" pageId="6" pageNumber="132">8</emphasis>
|
||
are thus responsible, at least in part, for the unpalatable taste of the fruiting bodies of
|
||
<taxonomicName id="4C004D19DF103F42A4323AB9FEE7FA6E" box="[272,361,1436,1456]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="6" pageNumber="132" phylum="Basidiomycota" rank="species" species="nobilis">
|
||
<emphasis id="B974EA88DF103F42A4323AB9FEE7FA6E" box="[272,361,1436,1456]" italics="true" pageId="6" pageNumber="132">R. nobilis</emphasis>
|
||
</taxonomicName>
|
||
, that quickly develops on the lips and tongue of a person who, unaware of its rather peculiar chemistry, bites the flesh of this mushroom. Actually, we believe that the complex patterns of sesquiterpenes formed at different times in the fruiting bodies of
|
||
<taxonomicName id="4C004D19DF103F42A4153929FE01F9FE" box="[311,399,1548,1568]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="6" pageNumber="132" phylum="Basidiomycota" rank="species" species="nobilis">
|
||
<emphasis id="B974EA88DF103F42A4153929FE01F9FE" box="[311,399,1548,1568]" italics="true" pageId="6" pageNumber="132">R. nobilis</emphasis>
|
||
</taxonomicName>
|
||
constitute a chemical defense system against microorganisms, parasites and predators (
|
||
<bibRefCitation id="EF914B6BDF103F42A78E390CFF5AF986" author="Sterner, O. & Bergman, R. & Kihlberg, J. & Wickberg, B." pageId="6" pageNumber="132" pagination="279 - 288" refId="ref11685" refString="Sterner, O., Bergman, R., Kihlberg, J., Wickberg, B., 1985. The Sesquiterpenes of Lactarius vellereus and their role in a proposed chemical defense system. J. Nat. Prod. 48, 279 - 288." type="journal article" year="1985">Sterner et al., 1985</bibRefCitation>
|
||
). Given the wide range of its biological activities (
|
||
<bibRefCitation id="EF914B6BDF103F42A57D3944FEE0F9AA" author="Vidari, G. & Vita-Finzi, P." box="[95,366,1633,1652]" pageId="6" pageNumber="132" pagination="152 - 206" refId="ref11924" refString="Vidari, G., Vita-Finzi, P., 1995. Sesquiterpenes and other secondary metabolites of the genus Lactarius (Basidiomycetes): chemistry and biological activity. In: Atta-ur-Rahman (Ed.), Studies in natural product chemistry structure and chemistry, vol. 17. Elsevier, Amsterdam, pp. 152 - 206." type="book chapter" year="1995">Vidari and Vita-Finzi, 1995</bibRefCitation>
|
||
) and its formation from tasteless ester
|
||
<quantity id="4CF89B7FDF103F42A5753958FF06F94E" box="[87,136,1661,1680]" metricMagnitude="-2" metricUnit="m" metricValue="2.54" pageId="6" pageNumber="132" unit="in" value="1.0">
|
||
<emphasis id="B974EA88DF103F42A5753958FFEAF94E" bold="true" box="[87,100,1661,1680]" pageId="6" pageNumber="132">1</emphasis>
|
||
in
|
||
</quantity>
|
||
a few seconds after injury to mushroom tissues, the dialdehyde velleral
|
||
<emphasis id="B974EA88DF103F42A40639BCFEBFF972" bold="true" box="[292,305,1689,1708]" pageId="6" pageNumber="132">3</emphasis>
|
||
is likely to be the main component of the deterrence machinery in
|
||
<taxonomicName id="4C004D19DF103F42A4753996FE21F919" box="[343,431,1715,1735]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="6" pageNumber="132" phylum="Basidiomycota" rank="species" species="nobilis">
|
||
<emphasis id="B974EA88DF103F42A4753996FE21F919" box="[343,431,1715,1735]" italics="true" pageId="6" pageNumber="132">R. nobilis</emphasis>
|
||
</taxonomicName>
|
||
.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF103F42A55439F5FCFAFD05" blockId="6.[87,758,432,2015]" lastBlockId="6.[805,1474,182,815]" pageId="6" pageNumber="132">
|
||
The existence of a chemical defense system in higher mushrooms is not an oddity. Indeed, like plants, fungi have evolved multivaried defense strategies in order to protect themselves against feeding mammals, including humans, insects, and parasites. So far, two different
|
||
<typeStatus id="54BB8838DF103F42A4453865FE13F88D" box="[359,413,1856,1875]" pageId="6" pageNumber="132">types</typeStatus>
|
||
of chemical defense mechanisms widely occur in higher mushrooms (
|
||
<bibRefCitation id="EF914B6BDF103F42A4FA3879FDE3F8B1" author="Spiteller, P." box="[472,621,1884,1903]" pageId="6" pageNumber="132" pagination="9100 - 9110" refId="ref11603" refString="Spiteller, P., 2008. Chemical defense strategies of higher mushrooms. Chem. Eur. J. 14, 9100 - 9110." type="journal article" year="2008">Spiteller, 2008</bibRefCitation>
|
||
). A group of fungi, e.g. toxic
|
||
<taxonomicName id="4C004D19DF103F42A4223852FE2BF855" box="[256,421,1911,1931]" pageId="6" pageNumber="132">
|
||
<emphasis id="B974EA88DF103F42A4223852FEDCF855" box="[256,338,1911,1931]" italics="true" pageId="6" pageNumber="132">Amanita</emphasis>
|
||
species
|
||
</taxonomicName>
|
||
, use secondary metabolites, e.g. amanitins, that are present permanently in their bioactive form in the mushrooms. Other mushrooms, like the
|
||
<taxonomicName id="4C004D19DF103F42A754388AFD31F81D" box="[630,703,1967,1987]" class="Agaricomycetes" family="Russulaceae" genus="Russula" kingdom="Fungi" order="Russulales" pageId="6" pageNumber="132" phylum="Basidiomycota" rank="genus">
|
||
<emphasis id="B974EA88DF103F42A754388AFD31F81D" box="[630,703,1967,1987]" italics="true" pageId="6" pageNumber="132">Russula</emphasis>
|
||
</taxonomicName>
|
||
and
|
||
<taxonomicName id="4C004D19DF103F42A57538EFFF73F800" box="[87,253,1994,2014]" pageId="6" pageNumber="132">
|
||
<emphasis id="B974EA88DF103F42A57538EFFF20F800" box="[87,174,1994,2014]" italics="true" pageId="6" pageNumber="132">Lactarius</emphasis>
|
||
species
|
||
</taxonomicName>
|
||
have elaborated a binary weapon system, namely wound-induced mechanisms relying on the enzymatic conversion of inactive precursors to the active agents, which occurs only transiently upon activation by an injury. It is interesting to note that
|
||
<taxonomicName id="4C004D19DF103F42A6073E2FFC11FEC3" authorityName="Lotsy" authorityYear="1907" box="[805,927,266,285]" class="Agaricomycetes" family="Russulaceae" kingdom="Fungi" order="Russulales" pageId="6" pageNumber="132" phylum="Basidiomycota" rank="family">Russulaceae</taxonomicName>
|
||
species have evolved, as components of their ammunition systems, not only sesquiterpenes belonging to the marasmane–lactarane cascade (
|
||
<bibRefCitation id="EF914B6BDF103F42A1493E67FA06FE8B" author="Daniewski, W. M. & Vidari, G." box="[1131,1416,322,341]" pageId="6" pageNumber="132" pagination="69 - 171" refId="ref10394" refString="Daniewski, W. M., Vidari, G., 1999. Constituents of Lactarius (mushrooms). In: Herz, W., Falk, H., Kirby, G. W., Moore, R. E., Tamm, C. H. (Eds.), Fortschritte der Chemie organischer Naturstoffe, vol. 77. Springer, Wien - New York, pp. 69 - 171." type="book chapter" year="1999">Daniewski and Vidari, 1999</bibRefCitation>
|
||
), like those described in this paper, but also guaiane, farnesane, drimane, caryophyllane, and other classes of terpenoids, depending on the species (
|
||
<bibRefCitation id="EF914B6BDF103F42A6583EB0FB04FE76" author="Vidari, G. & Vita-Finzi, P." box="[890,1162,405,424]" pageId="6" pageNumber="132" pagination="152 - 206" refId="ref11924" refString="Vidari, G., Vita-Finzi, P., 1995. Sesquiterpenes and other secondary metabolites of the genus Lactarius (Basidiomycetes): chemistry and biological activity. In: Atta-ur-Rahman (Ed.), Studies in natural product chemistry structure and chemistry, vol. 17. Elsevier, Amsterdam, pp. 152 - 206." type="book chapter" year="1995">Vidari and Vita-Finzi, 1995</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF103F42A1B73EB3FAF1FE76" author="Sterner, O. & Anke, H." box="[1173,1407,405,425]" pageId="6" pageNumber="132" pagination="39 - 52" refId="ref11777" refString="Sterner, O., Anke, H., 1995. Toxic terpenoids isolated from higher fungi. Czech Mmycol. 48, 39 - 52." type="journal article" year="1995">Sterner and Anke, 1995</bibRefCitation>
|
||
). Even mixed phenolic/terpenoid metabolites are present in the chemical defense machinery of a few
|
||
<taxonomicName id="4C004D19DF103F42A16F3EE9FB7BFE3E" box="[1101,1269,460,480]" pageId="6" pageNumber="132">
|
||
<emphasis id="B974EA88DF103F42A16F3EE9FB2AFE3E" box="[1101,1188,460,480]" italics="true" pageId="6" pageNumber="132">Lactarius</emphasis>
|
||
species
|
||
</taxonomicName>
|
||
(
|
||
<bibRefCitation id="EF914B6BDF103F42A0243EEBFCD2FE22" author="De Bernardi, M. & Vidari, G. & Vita-Finzi, P. & Fronza, G." pageId="6" pageNumber="132" pagination="7331 - 7344" refId="ref10475" refString="De Bernardi, M., Vidari, G., Vita-Finzi, P., Fronza, G., 1992. The chemistry of Lactarius fuliginosus and Lactarius picinus. Tetrahedron 48, 7331 - 7344." type="journal article" year="1992">De Bernardi et al., 1992</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="EF914B6BDF103F42A64E3ECCFBD5FE22" author="Takahashi, A. & Kusano, G. & Ohta, T. & Nozoe, S." box="[876,1115,489,508]" pageId="6" pageNumber="132" pagination="2032 - 2033" refId="ref11805" refString="Takahashi, A., Kusano, G., Ohta, T., Nozoe, S., 1993. Revised structures of flavidulos constituents of Lactarius flavidulus Imai, and the structure of flavidulol D. Chem. Pharm. Bull. 41, 2032 - 2033." type="journal article" year="1993">Takahashi et al., 1993</bibRefCitation>
|
||
). Contrary to the constitutive or wound-activated chemical defense mechanisms, so far little is known about the presence in higher mushrooms of an induced defense mechanism, that involves the activation of genes and an induction of the
|
||
<emphasis id="B974EA88DF103F42A6F43D7DFBABFDB2" box="[982,1061,600,620]" italics="true" pageId="6" pageNumber="132">de novo</emphasis>
|
||
biosynthesis of defense compounds. In striking contrast, induced chemical defense is widespread in plants (
|
||
<bibRefCitation id="EF914B6BDF103F42A60F3DB4FC4CFD7A" author="Spiteller, P." box="[813,962,657,676]" pageId="6" pageNumber="132" pagination="9100 - 9110" refId="ref11603" refString="Spiteller, P., 2008. Chemical defense strategies of higher mushrooms. Chem. Eur. J. 14, 9100 - 9110." type="journal article" year="2008">Spiteller, 2008</bibRefCitation>
|
||
) and this may represent a significant metabolic advantage for living organisms and an important evolutionary marker.
|
||
</paragraph>
|
||
<paragraph id="8BBF369ADF103F42A6663DC1FCDEFCF1" blockId="6.[805,1474,182,815]" pageId="6" pageNumber="132">
|
||
Compounds
|
||
<emphasis id="B974EA88DF103F42A6E13DC1FC55FD29" bold="true" box="[963,987,740,759]" pageId="6" pageNumber="132">7a</emphasis>
|
||
and
|
||
<emphasis id="B974EA88DF103F42A12D3DC1FBCCFD29" bold="true" box="[1039,1090,740,760]" pageId="6" pageNumber="132">9–12</emphasis>
|
||
are not significantly cytotoxic, showing an IC
|
||
<quantity id="4CF89B7FDF103F42A65F3C2CFC24FCCD" box="[893,938,768,789]" metricMagnitude="0" metricUnit="m" metricValue="1.27" pageId="6" pageNumber="132" unit="in" value="50.0">
|
||
<subScript id="178434DFDF103F42A65F3C2CFC01FCCB" attach="left" box="[893,911,777,789]" fontSize="5" pageId="6" pageNumber="132">50</subScript>
|
||
in
|
||
</quantity>
|
||
the range of 25–30 µg/mL against a H460 tumor cell line.
|
||
</paragraph>
|
||
</subSubSection>
|
||
</subSection>
|
||
</treatment>
|
||
</document> |