369 lines
33 KiB
XML
369 lines
33 KiB
XML
<document id="1D8A695478CFD318A3EB708150C99FD5" ID-DOI="10.1016/j.phytochem.2014.11.015" ID-ISSN="1873-3700" ID-Zenodo-Dep="10485784" IM.bibliography_approvedBy="diego" IM.illustrations_approvedBy="diego" IM.materialsCitations_approvedBy="diego" IM.metadata_approvedBy="felipe" IM.tables_approvedBy="diego" IM.taxonomicNames_approvedBy="diego" IM.treatments_approvedBy="diego" checkinTime="1704946437846" checkinUser="felipe" docAuthor="Casero, Carina N., Oberti, Juan C., Orozco, Clara I., Cárdenas, Alejandro, Brito, Iván, Barboza, Gloria E. & Nicotra, Viviana E." docDate="2015" docId="2E4652478B4BFFEAFFB4FEB0EE5B164D" docLanguage="en" docName="Phytochemistry.110.83-90.pdf" docOrigin="Phytochemistry 110" docSource="http://dx.doi.org/10.1016/j.phytochem.2014.11.015" docStyle="DocumentStyle:9E596C34F4E94307D29315B03ACE1007.6:Phytochemistry.2014-2019.journal_article" docStyleId="9E596C34F4E94307D29315B03ACE1007" docStyleName="Phytochemistry.2014-2019.journal_article" docStyleVersion="6" docTitle="Deprea bitteriana N. W. Sawyer & Benitez" docType="treatment" docVersion="4" lastPageNumber="84" masterDocId="D27F2A3F8B4AFFE8FFE3FFB9EF65130D" masterDocTitle="Withanolides from three species of the genus Deprea (Solanaceae). Chemotaxonomical considerations" masterLastPageNumber="90" masterPageNumber="83" pageNumber="84" updateTime="1705580942250" updateUser="diego">
|
||
<mods:mods id="F1400CFCCEBEA356D6E2BF03631AD265" xmlns:mods="http://www.loc.gov/mods/v3">
|
||
<mods:titleInfo id="3627B8D19005F711CB616CC3B4B6344E">
|
||
<mods:title id="DC556EBD3A77D7EB8119C57422380E0E">Withanolides from three species of the genus Deprea (Solanaceae). Chemotaxonomical considerations</mods:title>
|
||
</mods:titleInfo>
|
||
<mods:name id="9B33B350F8963F9DA28718E21E7580BF" type="personal">
|
||
<mods:role id="0585182910A9C48368EB8E5B65EB7905">
|
||
<mods:roleTerm id="70983F37F1317B33142948FC616A1C3C">Author</mods:roleTerm>
|
||
</mods:role>
|
||
<mods:namePart id="ABC271CA952ADE9F9B3211949E732319">Casero, Carina N.</mods:namePart>
|
||
<mods:affiliation id="2C8C0560991DCF74009DBEBE9BB1C4CA">Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Instituto Multidisciplinario de Biología Vegetal (IMBIV-CONICET), Casilla de Correo 495, 5000 Córdoba, Argentina</mods:affiliation>
|
||
</mods:name>
|
||
<mods:name id="7DC38731371AAFBA7EB465BE3E5FD614" type="personal">
|
||
<mods:role id="0CF42740A88F4F5B91F60F0FB5B0489A">
|
||
<mods:roleTerm id="CCDA7F394C16745C83B304388870048C">Author</mods:roleTerm>
|
||
</mods:role>
|
||
<mods:namePart id="9330A1C6E9B30EF7B1C3DD982F83971A">Oberti, Juan C.</mods:namePart>
|
||
</mods:name>
|
||
<mods:name id="BFD31D524C57FFE47DC3FD84FE199C2E" type="personal">
|
||
<mods:role id="51F3396A22315719363E282717DF1CAA">
|
||
<mods:roleTerm id="83420CE40413DF7B68AB38B157092300">Author</mods:roleTerm>
|
||
</mods:role>
|
||
<mods:namePart id="4397052D977ED0D7EB78A0C07907CA07">Orozco, Clara I.</mods:namePart>
|
||
</mods:name>
|
||
<mods:name id="2516D907DF184E698E140FFAD446D20A" type="personal">
|
||
<mods:role id="D9A6DAB5C4A043C03A1A4C736BDCB14B">
|
||
<mods:roleTerm id="5A33D5B6F24DD8943998EAF5FF3AFC80">Author</mods:roleTerm>
|
||
</mods:role>
|
||
<mods:namePart id="B20CADEE3F9E946472C3634394BF4837">Cárdenas, Alejandro</mods:namePart>
|
||
</mods:name>
|
||
<mods:name id="0BDDDF6A0428528248CEE8B1E007CF4B" type="personal">
|
||
<mods:role id="7DEE06AF033A4B7894FB8084D9E0CDF1">
|
||
<mods:roleTerm id="3CFC6930E0E8BBF55E80FEBD747B9478">Author</mods:roleTerm>
|
||
</mods:role>
|
||
<mods:namePart id="5E3F2D1B24E2C437525D048AAC3349DA">Brito, Iván</mods:namePart>
|
||
</mods:name>
|
||
<mods:name id="87EEA8E8B4CE0916367EE8C804982F88" type="personal">
|
||
<mods:role id="093A507A608AEB55E01EB45692FFE5EC">
|
||
<mods:roleTerm id="A9F2D572BAA2D72564C3CD24FF9372E5">Author</mods:roleTerm>
|
||
</mods:role>
|
||
<mods:namePart id="07D0DB62D47F4E7661B8EBE0986CC529">Barboza, Gloria E.</mods:namePart>
|
||
</mods:name>
|
||
<mods:name id="511D6E8035AADB87FDFBD83C1D6AC2A1" type="personal">
|
||
<mods:role id="F706946AD155D4B2B28FF80639C8B720">
|
||
<mods:roleTerm id="CC381D7DCA9D0D48A4AB9D78DFDE3644">Author</mods:roleTerm>
|
||
</mods:role>
|
||
<mods:namePart id="8ECF4066C3231CCCF9F51AE320B7D9B3">Nicotra, Viviana E.</mods:namePart>
|
||
</mods:name>
|
||
<mods:typeOfResource id="B1269C735E767429462B77C17D5AC1A4">text</mods:typeOfResource>
|
||
<mods:relatedItem id="1C60FE23EB296822D876949393DFF3AD" type="host">
|
||
<mods:titleInfo id="961D602C22A92023F65C3012A4FEEA61">
|
||
<mods:title id="E3C0B1F8ED09B1BB45D6D6FE31293DBA">Phytochemistry</mods:title>
|
||
</mods:titleInfo>
|
||
<mods:part id="22AEA7EEDFC0D3BA6306D056C1DBF27D">
|
||
<mods:date id="FF4DAC1528E685C2FBE2C2EB91B3402B">2015</mods:date>
|
||
<mods:detail id="6D18160D43FAB23105D7E3CF6AEBFC3C" type="pubDate">
|
||
<mods:number id="0844CA55AA765D2039C8C9D0DAB4DBE3">2015-02-28</mods:number>
|
||
</mods:detail>
|
||
<mods:detail id="62ED6B14229F308DE09136F8DAEE43E6" type="volume">
|
||
<mods:number id="22540E18E57F0BAE1BB0C7F5C2AECDE9">110</mods:number>
|
||
</mods:detail>
|
||
<mods:extent id="D256A5E0B4B628D28546B5490CA412CB" unit="page">
|
||
<mods:start id="E6A7EE35CAD69E928FB6B63277A9A1DF">83</mods:start>
|
||
<mods:end id="64938879E77EF363F24D0E2E0F5E92C3">90</mods:end>
|
||
</mods:extent>
|
||
</mods:part>
|
||
</mods:relatedItem>
|
||
<mods:location id="C8A567E4E9F523C3FDF58003E9510E09">
|
||
<mods:url id="9B102F05F9EC068332DA0C0AA10384EE">http://dx.doi.org/10.1016/j.phytochem.2014.11.015</mods:url>
|
||
</mods:location>
|
||
<mods:classification id="A6FD5E34A4EBD04C5F3914788C43FE67">journal article</mods:classification>
|
||
<mods:identifier id="C9FF0BBD7016EBCA548F6BA3F33346F4" type="DOI">10.1016/j.phytochem.2014.11.015</mods:identifier>
|
||
<mods:identifier id="2A7FEAFF8DC3BA30BBB1CD77DA806691" type="ISSN">1873-3700</mods:identifier>
|
||
<mods:identifier id="65D7B19EC829B2EBB8CF6B65E7849169" type="Zenodo-Dep">10485784</mods:identifier>
|
||
</mods:mods>
|
||
<treatment id="2E4652478B4BFFEAFFB4FEB0EE5B164D" LSID="urn:lsid:plazi:treatment:2E4652478B4BFFEAFFB4FEB0EE5B164D" httpUri="http://treatment.plazi.org/id/2E4652478B4BFFEAFFB4FEB0EE5B164D" lastPageId="2" lastPageNumber="84" pageId="1" pageNumber="84">
|
||
<subSubSection id="EEF5B0DA8B4BFFE9FFB4FEB0ED601210" box="[87,517,265,285]" pageId="1" pageNumber="84" type="nomenclature">
|
||
<paragraph id="A650E3518B4BFFE9FFB4FEB0ED601210" blockId="1.[87,517,265,285]" box="[87,517,265,285]" pageId="1" pageNumber="84">
|
||
<heading id="FD18543D8B4BFFE9FFB4FEB0ED601210" box="[87,517,265,285]" fontSize="36" level="2" pageId="1" pageNumber="84" reason="3">
|
||
<emphasis id="949B3F438B4BFFE9FFB4FEB0ED601210" box="[87,517,265,285]" italics="true" pageId="1" pageNumber="84">
|
||
2.1. Withanolides isolated from
|
||
<taxonomicName id="61EF98D28B4BFFE9FE6FFEB0ED601210" ID-CoL="6CLS6" authority="(Werderm.) N. W. Sawyer & Benitez" authorityName="N. W. Sawyer & Benitez" baseAuthorityName="Werderm." box="[396,517,265,285]" class="Magnoliopsida" family="Solanaceae" genus="Deprea" kingdom="Plantae" order="Solanales" pageId="1" pageNumber="84" phylum="Tracheophyta" rank="species" species="bitteriana">D. bitteriana</taxonomicName>
|
||
</emphasis>
|
||
</heading>
|
||
</paragraph>
|
||
</subSubSection>
|
||
<subSubSection id="EEF5B0DA8B4BFFEAFF95FEF8EE5B164D" lastPageId="2" lastPageNumber="85" pageId="1" pageNumber="84" type="description">
|
||
<paragraph id="A650E3518B4BFFE9FF95FEF8ED4D1139" blockId="1.[87,757,321,1011]" pageId="1" pageNumber="84">
|
||
<taxonomicName id="61EF98D28B4BFFE9FF95FEF8EF8A1258" box="[118,239,321,341]" class="Magnoliopsida" family="Solanaceae" genus="Deprea" kingdom="Plantae" order="Solanales" pageId="1" pageNumber="84" phylum="Tracheophyta" rank="species" species="bitteriana">
|
||
<emphasis id="949B3F438B4BFFE9FF95FEF8EF8A1258" box="[118,239,321,341]" italics="true" pageId="1" pageNumber="84">D. bitteriana</emphasis>
|
||
</taxonomicName>
|
||
afforded the new compounds withaphysalins V (
|
||
<emphasis id="949B3F438B4BFFE9FD03FEFBED881258" bold="true" box="[736,749,322,341]" pageId="1" pageNumber="84">1</emphasis>
|
||
) and W (
|
||
<emphasis id="949B3F438B4BFFE9FF53FEE7EFD8127C" bold="true" box="[176,189,350,369]" pageId="1" pageNumber="84">2</emphasis>
|
||
). Withaphysalins are characterized by oxygenation at the Me(18) group to the level of an alcohol, aldehyde, or acid functioality, which in the latter two cases can lead to cyclization with OH-C(20) to yield a hemiacetal or a lactone. The hemiacetal arrangement is characterized by the absence of the methyl-18
|
||
<superScript id="519A4E198B4BFFE9FD38FE70ED8112D8" attach="right" box="[731,740,457,469]" fontSize="5" pageId="1" pageNumber="84">1</superScript>
|
||
H NMR singlet at low-frequency shift, and by the appearance of two methine carbynolic resonances, indicating the presence of
|
||
<emphasis id="949B3F438B4BFFE9FFB4FD99EF011139" box="[87,100,544,564]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
/
|
||
<emphasis id="949B3F438B4BFFE9FF8FFD99EF121139" box="[108,119,544,564]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
mixtures of epimeric hemiacetals at C-18.
|
||
</paragraph>
|
||
<paragraph id="A650E3518B4BFFE9FF95FD84ED9010FF" blockId="1.[87,757,321,1011]" pageId="1" pageNumber="84">
|
||
The HRESIMS of withaphysalin V (
|
||
<emphasis id="949B3F438B4BFFE9FE3DFD84EE8E115D" bold="true" box="[478,491,573,592]" pageId="1" pageNumber="84">1</emphasis>
|
||
) showed a molecular ion [M+Na]
|
||
<superScript id="519A4E198B4BFFE9FF40FDECEFC9116C" attach="left" box="[163,172,597,609]" fontSize="5" pageId="1" pageNumber="84">+</superScript>
|
||
at
|
||
<emphasis id="949B3F438B4BFFE9FF2CFDE1EF871161" box="[207,226,600,620]" italics="true" pageId="1" pageNumber="84">m</emphasis>
|
||
/
|
||
<emphasis id="949B3F438B4BFFE9FF0AFDE1EF961161" box="[233,243,600,620]" italics="true" pageId="1" pageNumber="84">z</emphasis>
|
||
491.2383, corresponding to an elemental formula of C
|
||
<subScript id="3A6BE1148B4BFFE9FF61FDC7EFF01187" attach="both" box="[130,149,638,650]" fontSize="5" pageId="1" pageNumber="84">28</subScript>
|
||
H
|
||
<subScript id="3A6BE1148B4BFFE9FF46FDC7EFDD1187" attach="right" box="[165,184,638,650]" fontSize="5" pageId="1" pageNumber="84">36</subScript>
|
||
O
|
||
<subScript id="3A6BE1148B4BFFE9FF24FDC7EFB51187" attach="both" box="[199,208,638,650]" fontSize="5" pageId="1" pageNumber="84">6</subScript>
|
||
Na. Inspection of the 1D and 2D NMR spectroscopic data indicated that compound
|
||
<emphasis id="949B3F438B4BFFE9FE77FD29EEC411AE" bold="true" box="[404,417,656,675]" pageId="1" pageNumber="84">1</emphasis>
|
||
possessed rings C and D, as well as the side-chain closely related to those of withaphysalins B [isolated for the first time from
|
||
<taxonomicName id="61EF98D28B4BFFE9FE95FD7EED8C11D6" authority="(Glotter et al., 1975)" baseAuthorityName="Glotter" baseAuthorityYear="1975" box="[374,745,711,732]" class="Magnoliopsida" family="Solanaceae" genus="Physalis" kingdom="Plantae" order="Solanales" pageId="1" pageNumber="84" phylum="Tracheophyta" rank="species" species="minima">
|
||
<emphasis id="949B3F438B4BFFE9FE95FD7EED7111D6" box="[374,532,711,731]" italics="true" pageId="1" pageNumber="84">Physalis minima</emphasis>
|
||
(
|
||
<bibRefCitation id="C27E9EA08B4BFFE9FDC1FD71ED8511D6" author="Glotter, E. & Kirson, I. & Abraham, A. & Sethi, P. D. & Subramanian, S. S." box="[546,736,712,732]" pageId="1" pageNumber="84" pagination="1370 - 1374" refId="ref8728" refString="Glotter, E., Kirson, I., Abraham, A., Sethi, P. D., Subramanian, S. S., 1975. Steroidal constituents of Physalis minima (Solanaceae). J. Chem. Soc. Perkin 1 (14), 1370 - 1374." type="journal article" year="1975">Glotter et al., 1975</bibRefCitation>
|
||
)
|
||
</taxonomicName>
|
||
], F, and G [isolated for the first time from
|
||
<taxonomicName id="61EF98D28B4BFFE9FE0EFD5AEFB5101E" authority="(Misico et al., 2000)" baseAuthorityName="Misico" baseAuthorityYear="2000" class="Magnoliopsida" family="Solanaceae" genus="Eriolarynx" kingdom="Plantae" order="Solanales" pageId="1" pageNumber="84" phylum="Tracheophyta" rank="species" species="lorentzii">
|
||
<emphasis id="949B3F438B4BFFE9FE0EFD5AEDC011FA" box="[493,677,739,759]" italics="true" pageId="1" pageNumber="84">Eriolarynx lorentzii</emphasis>
|
||
(
|
||
<bibRefCitation id="C27E9EA08B4BFFE9FD50FD5DEFA2101E" author="Misico, R. I. & Gil, R. R. & Oberti, J. C. & Veleiro, A. S. & Burton, G." pageId="1" pageNumber="84" pagination="1329 - 1332" refId="ref9242" refString="Misico, R. I., Gil, R. R., Oberti, J. C., Veleiro, A. S., Burton, G., 2000. Withanolides from Vassobia lorentzii. J. Nat. Prod. 63, 1329 - 1332." type="journal article" year="2000">Misico et al., 2000</bibRefCitation>
|
||
)
|
||
</taxonomicName>
|
||
]. The absence of a signal for
|
||
<collectingCountry id="DEF8A3C18B4BFFE9FE1BFCB9ED73101E" box="[504,534,768,787]" name="Switzerland" pageId="1" pageNumber="84">CH</collectingCountry>
|
||
<subScript id="3A6BE1148B4BFFE9FDF6FCB0ED7B1018" attach="left" box="[533,542,777,789]" fontSize="5" pageId="1" pageNumber="84">3</subScript>
|
||
-18 and the presence of two proton resonances at
|
||
<emphasis id="949B3F438B4BFFE9FE96FCA5EEE51022" bold="true" box="[373,384,796,815]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
5.18 (1H,
|
||
<emphasis id="949B3F438B4BFFE9FE04FCA2ED6F1022" box="[487,522,795,815]" italics="true" pageId="1" pageNumber="84">br s</emphasis>
|
||
) (50%) and 5.31 (1H,
|
||
<emphasis id="949B3F438B4BFFE9FD03FCA2EF051046" italics="true" pageId="1" pageNumber="84">br s</emphasis>
|
||
) (50%) (
|
||
<tableCitation id="EB6DD6EA8B4BFFE9FF55FC81EE641046" box="[182,257,824,843]" captionStart="Table 1" captionStartId="2.[265,309,183,197]" captionTargetPageId="2" captionText="Table 1 1H NMR spectroscopic data of compounds 1–3 in CDCl. a 3" pageId="1" pageNumber="84">Table 1</tableCitation>
|
||
) were indicative of a lactol functionality at C-18 and were assigned to the 18
|
||
<emphasis id="949B3F438B4BFFE9FE9EFCEAEEEF106A" box="[381,394,851,871]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
and 18
|
||
<emphasis id="949B3F438B4BFFE9FE3BFCEAEE86106A" box="[472,483,851,871]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
epimers, respectively. The
|
||
<superScript id="519A4E198B4BFFE9FFB4FCD5EF0F1075" attach="right" box="[87,106,876,888]" fontSize="5" pageId="1" pageNumber="84">13</superScript>
|
||
C NMR spectrum showed methine signals at
|
||
<emphasis id="949B3F438B4BFFE9FD8DFCC9ED1C108E" bold="true" box="[622,633,880,899]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
101.3 and 103.9 ppm (C-18
|
||
<emphasis id="949B3F438B4BFFE9FEE8FC32EE7D1092" box="[267,280,907,927]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
/
|
||
<emphasis id="949B3F438B4BFFE9FEC3FC32EE4E1092" box="[288,299,907,927]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
) and resonances at
|
||
<emphasis id="949B3F438B4BFFE9FE1DFC35ED6C1092" bold="true" box="[510,521,908,927]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
58.1/58.9,
|
||
<emphasis id="949B3F438B4BFFE9FD9DFC35EDEC1092" bold="true" box="[638,649,908,927]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
56.8/56.8, and
|
||
<emphasis id="949B3F438B4BFFE9FF6AFC11EFF110B6" bold="true" box="[137,148,936,955]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
84.9/85.2 assigned at C-13
|
||
<emphasis id="949B3F438B4BFFE9FE2BFC1FEEB010B7" box="[456,469,934,954]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
/
|
||
<emphasis id="949B3F438B4BFFE9FE3FFC1FEE8210B7" box="[476,487,934,954]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
, C-17
|
||
<emphasis id="949B3F438B4BFFE9FDD7FC1FED2410B7" box="[564,577,934,954]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
/
|
||
<emphasis id="949B3F438B4BFFE9FDABFC1FED3610B7" box="[584,595,934,954]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
, and C-20
|
||
<emphasis id="949B3F438B4BFFE9FD32FC1FEDBB10B7" box="[721,734,934,954]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
/
|
||
<emphasis id="949B3F438B4BFFE9FD06FC1FED9510B7" box="[741,752,934,954]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
, respectively, thus confirming a five-membered lactol ring (
|
||
<tableCitation id="EB6DD6EA8B4BFFE9FD43FC7AED8D10DA" box="[672,744,963,983]" captionStart="Table 3" captionStartId="4.[114,158,183,197]" captionTargetPageId="4" captionText="Table 3 13C NMR spectroscopic data of compounds 18 in CDCl. a 3" pageId="1" pageNumber="84">Table 3</tableCitation>
|
||
). The doublet of doublets at
|
||
<emphasis id="949B3F438B4BFFE9FE82FC59EE0910FE" bold="true" box="[353,364,992,1011]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
4.46/4.54 (H-22
|
||
<emphasis id="949B3F438B4BFFE9FDF6FC67ED4710FF" box="[533,546,990,1010]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
/
|
||
<emphasis id="949B3F438B4BFFE9FDCAFC67ED5110FF" box="[553,564,990,1010]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
), together with the
|
||
</paragraph>
|
||
<paragraph id="A650E3518B4BFFE9FCC6FF0EECEF11D6" blockId="1.[805,1475,182,1011]" pageId="1" pageNumber="84">
|
||
two three-proton singlets at
|
||
<emphasis id="949B3F438B4BFFE9FBBCFF0EEB0F13C7" bold="true" box="[1119,1130,183,202]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
1.88 (H
|
||
<subScript id="3A6BE1148B4BFFE9FB24FF06EBB513C6" attach="left" box="[1223,1232,191,203]" fontSize="5" pageId="1" pageNumber="84">3</subScript>
|
||
-27) and 1.95 (H
|
||
<subScript id="3A6BE1148B4BFFE9FA6AFF06EAF713C6" attach="left" box="[1417,1426,191,203]" fontSize="5" pageId="1" pageNumber="84">3</subScript>
|
||
-28), indicated the presence of a
|
||
<emphasis id="949B3F438B4BFFE9FBAFFF6BEB3213E8" bold="true" box="[1100,1111,210,229]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
lactone as a side-chain. The resonances at
|
||
<emphasis id="949B3F438B4BFFE9FC74FF57ECC7120C" bold="true" box="[919,930,238,257]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
80.6/80.4 (C-22
|
||
<emphasis id="949B3F438B4BFFE9FBBEFF54EB0F120C" box="[1117,1130,237,257]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
/
|
||
<emphasis id="949B3F438B4BFFE9FB91FF54EB18120C" box="[1138,1149,237,257]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
), 148.0/148.8 (C-24
|
||
<emphasis id="949B3F438B4BFFE9FABCFF54EA09120C" box="[1375,1388,237,257]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
and
|
||
<emphasis id="949B3F438B4BFFE9FA49FF54EAD0120C" box="[1450,1461,237,257]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
), 121.9/122.2 (C-25
|
||
<emphasis id="949B3F438B4BFFE9FC00FEB0EC951210" box="[995,1008,265,285]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
and
|
||
<emphasis id="949B3F438B4BFFE9FBC6FEB0EB551210" box="[1061,1072,265,285]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
), 165.6/165.7 (C-26
|
||
<emphasis id="949B3F438B4BFFE9FAE0FEB0EA751210" box="[1283,1296,265,285]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
and
|
||
<emphasis id="949B3F438B4BFFE9FAA7FEB0EA2A1210" box="[1348,1359,265,285]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
), 12.4/12.5 (C-27
|
||
<emphasis id="949B3F438B4BFFE9FC87FE9CEC141234" box="[868,881,293,313]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
and
|
||
<emphasis id="949B3F438B4BFFE9FC45FE9CECD41234" box="[934,945,293,313]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
), and 20.4/20.5 (C-28
|
||
<emphasis id="949B3F438B4BFFE9FB7AFE9CEBC31234" box="[1177,1190,293,313]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
and
|
||
<emphasis id="949B3F438B4BFFE9FB38FE9CEB831234" box="[1243,1254,293,313]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
), observed in the
|
||
<superScript id="519A4E198B4BFFE9FA41FE9BEAD01223" attach="right" box="[1442,1461,290,302]" fontSize="5" pageId="1" pageNumber="84">13</superScript>
|
||
C NMR spectrum, were in agreement with a
|
||
<emphasis id="949B3F438B4BFFE9FB0CFEFBEB9F1258" bold="true" box="[1263,1274,322,341]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
lactone. Regarding rings A and B, the
|
||
<superScript id="519A4E198B4BFFE9FC15FEE3EC9A126B" attach="right" box="[1014,1023,346,358]" fontSize="5" pageId="1" pageNumber="84">1</superScript>
|
||
H NMR spectrum of the epimeric mixture showed characteristic signals of H-2, H-3, and H-6 hydrogens for a 1-oxo-2,5-withadienolide at
|
||
<emphasis id="949B3F438B4BFFE9FB8AFE2FEB1112A4" bold="true" box="[1129,1140,406,425]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
5.91 (
|
||
<emphasis id="949B3F438B4BFFE9FB5CFE2DEBB212A5" box="[1215,1239,404,424]" italics="true" pageId="1" pageNumber="84">dd</emphasis>
|
||
, H-2), 6.81/6.80 (
|
||
<emphasis id="949B3F438B4BFFE9FA7AFE2DEAD812A5" box="[1433,1469,404,424]" italics="true" pageId="1" pageNumber="84">ddd</emphasis>
|
||
, H-3), and 5.84/5.83 (
|
||
<emphasis id="949B3F438B4BFFE9FBF5FE09EB4C12C9" box="[1046,1065,432,452]" italics="true" pageId="1" pageNumber="84">m</emphasis>
|
||
, H-6), respectively (
|
||
<bibRefCitation id="C27E9EA08B4BFFE9FAF6FE08ECCB12ED" author="Ramacciotti, N. S. & Nicotra, V. E." pageId="1" pageNumber="84" pagination="1513 - 1515" refId="ref9437" refString="Ramacciotti, N. S., Nicotra, V. E., 2007. Withanolides from Jaborosa kurtzii. J. Nat. Prod. 70, 1513 - 1515." type="journal article" year="2007">Ramacciotti and Nicotra, 2007</bibRefCitation>
|
||
). The correlation found between H-6 with H-7 at
|
||
<emphasis id="949B3F438B4BFFE9FA54FE74EAA712ED" bold="true" box="[1463,1474,461,480]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
<quantity id="61174EB48B4BFFE9FCC6FE50EC0912F1" box="[805,876,489,508]" metricMagnitude="-1" metricUnit="m" metricValue="1.0033" pageId="1" pageNumber="84" unit="in" value="3.95">3.95 in</quantity>
|
||
the COSY spectrum suggested the hydroxy group to be at C-7. Olefinic resonances at
|
||
<emphasis id="949B3F438B4BFFE9FBDFFDBCEB221115" bold="true" box="[1084,1095,517,536]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
128.0, 144.9/144.6, 141.4/140.9, and 126.0/126.4, a carbonyl carbon at
|
||
<emphasis id="949B3F438B4BFFE9FB69FD98EBF01139" bold="true" box="[1162,1173,545,564]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
203.0/203.3 (C-1
|
||
<emphasis id="949B3F438B4BFFE9FAB0FD99EA051139" box="[1363,1376,544,564]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
/
|
||
<emphasis id="949B3F438B4BFFE9FA84FD99EA171139" box="[1383,1394,544,564]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
), and a carbynolic carbon at
|
||
<emphasis id="949B3F438B4BFFE9FBE6FD84EB75115D" bold="true" box="[1029,1040,573,592]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
64.5 (C-7
|
||
<emphasis id="949B3F438B4BFFE9FB66FD85EBF7115D" box="[1157,1170,572,592]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
/
|
||
<emphasis id="949B3F438B4BFFE9FB79FD85EBC0115D" box="[1178,1189,572,592]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
) were observed in the
|
||
<superScript id="519A4E198B4BFFE9FA41FD80EAD01148" attach="right" box="[1442,1461,569,581]" fontSize="5" pageId="1" pageNumber="84">13</superScript>
|
||
C NMR spectrum. The
|
||
<emphasis id="949B3F438B4BFFE9FBE3FDEFEB681161" bold="true" box="[1024,1037,598,620]" italics="true" pageId="1" pageNumber="84">OE</emphasis>
|
||
orientation of the hydroxy group at C-7 was established by a NOESY experiment. The NOE observed between H-7 and H-8
|
||
<emphasis id="949B3F438B4BFFE9FBE4FD36EB7111AE" box="[1031,1044,655,675]" italics="true" pageId="1" pageNumber="84">R</emphasis>
|
||
/
|
||
<emphasis id="949B3F438B4BFFE9FBFFFD36EB4211AE" box="[1052,1063,655,675]" italics="true" pageId="1" pageNumber="84">S</emphasis>
|
||
(
|
||
<emphasis id="949B3F438B4BFFE9FBD6FD28EB2511A9" bold="true" box="[1077,1088,657,676]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
1.51/1.92) indicated the
|
||
<emphasis id="949B3F438B4BFFE9FADCFD28EA2E11A9" bold="true" box="[1343,1355,657,676]" pageId="1" pageNumber="84">b</emphasis>
|
||
orientation of H-7. Accordingly, the structure of compound
|
||
<emphasis id="949B3F438B4BFFE9FAE8FD15EA7D11B2" bold="true" box="[1291,1304,684,703]" pageId="1" pageNumber="84">1</emphasis>
|
||
was determined as shown.
|
||
</paragraph>
|
||
<paragraph id="A650E3518B4BFFEAFCA7FD5DEE5B164D" blockId="1.[805,1475,182,1011]" lastBlockId="2.[113,783,1154,1344]" lastPageId="2" lastPageNumber="85" pageId="1" pageNumber="84">
|
||
The molecular formula of withaphysalin
|
||
<collectionCode id="C0FE7B948B4BFFE9FB3CFD5CEB9311F5" box="[1247,1270,741,760]" country="Austria" lsid="urn:lsid:biocol.org:col:15588" name="Naturhistorisches Museum Wien" pageId="1" pageNumber="84" type="Herbarium">W</collectionCode>
|
||
(
|
||
<emphasis id="949B3F438B4BFFE9FAE7FD5DEA7411FA" bold="true" box="[1284,1297,740,759]" pageId="1" pageNumber="84">2</emphasis>
|
||
) was determined by HRESIMS as
|
||
<specimenCode id="F6494B2A8B4BFFE9FC2BFCB9EC8D1018" box="[968,1000,768,789]" collectionCode="C" country="Denmark" name="University of Copenhagen" pageId="1" pageNumber="84" type="Herbarium">
|
||
C
|
||
<subScript id="3A6BE1148B4BFFE9FC36FCB0EC8D1018" attach="both" box="[981,1000,777,789]" fontSize="5" pageId="1" pageNumber="84">28</subScript>
|
||
</specimenCode>
|
||
<specimenCode id="F6494B2A8B4BFFE9FC0BFCB8EB6E1018" box="[1000,1035,769,789]" collectionCode="H" country="Finland" lsid="urn:lsid:biocol.org:col:15618" name="University of Helsinki" pageId="1" pageNumber="84" type="Herbarium">
|
||
H
|
||
<subScript id="3A6BE1148B4BFFE9FC1BFCB0EB6E1018" attach="both" box="[1016,1035,777,789]" fontSize="5" pageId="1" pageNumber="84">36</subScript>
|
||
</specimenCode>
|
||
<specimenCode id="F6494B2A8B4BFFE9FBE8FCB9EB411018" box="[1035,1060,768,789]" collectionCode="O" country="Norway" lsid="urn:lsid:biocol.org:col:13093" name="Botanical Museum - University of Oslo" pageId="1" pageNumber="84" type="Herbarium">
|
||
O
|
||
<subScript id="3A6BE1148B4BFFE9FBF8FCB0EB411018" attach="left" box="[1051,1060,777,789]" fontSize="5" pageId="1" pageNumber="84">6</subScript>
|
||
</specimenCode>
|
||
. Similar to
|
||
<emphasis id="949B3F438B4BFFE9FB7CFCB9EBC9101E" bold="true" box="[1183,1196,768,787]" pageId="1" pageNumber="84">1</emphasis>
|
||
, compound
|
||
<emphasis id="949B3F438B4BFFE9FACEFCB9EA5F101E" bold="true" box="[1325,1338,768,787]" pageId="1" pageNumber="84">2</emphasis>
|
||
was demonstrated to be a 1:1 epimeric mixture from its
|
||
<superScript id="519A4E198B4BFFE9FAE1FCA1EA6E1029" attach="right" box="[1282,1291,792,804]" fontSize="5" pageId="1" pageNumber="84">1</superScript>
|
||
<collectionCode id="C0FE7B948B4BFFE9FAE8FCA5EA7E1022" box="[1291,1307,796,815]" country="Finland" lsid="urn:lsid:biocol.org:col:15618" name="University of Helsinki" pageId="1" pageNumber="84" type="Herbarium">H</collectionCode>
|
||
<collectionCode id="C0FE7B948B4BFFE9FAC7FCA5EA331022" box="[1316,1366,796,815]" country="Netherlands" httpUri="http://grbio.org/cool/jyde-k516" name="Natuurhistorisch Museum" pageId="1" pageNumber="84">NMR</collectionCode>
|
||
spectrum, which showed characteristic H-18 epimeric protons resonating at
|
||
<emphasis id="949B3F438B4BFFE9FCC6FCEDEC55106A" bold="true" box="[805,816,852,871]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
<geoCoordinate id="C3DB85968B4BFFE9FCDAFCEDEC12106A" box="[825,887,851,871]" degrees="5.21" direction="south" orientation="latitude" pageId="1" pageNumber="84" precision="555" value="-5.21">
|
||
5.21
|
||
<emphasis id="949B3F438B4BFFE9FC8DFCEAEC12106A" box="[878,887,851,871]" italics="true" pageId="1" pageNumber="84">s</emphasis>
|
||
</geoCoordinate>
|
||
and
|
||
<geoCoordinate id="C3DB85968B4BFFE9FC4CFCEDEC88106A" box="[943,1005,851,871]" degrees="5.31" direction="south" orientation="latitude" pageId="1" pageNumber="84" precision="555" value="-5.31">
|
||
5.31
|
||
<emphasis id="949B3F438B4BFFE9FC07FCEAEC88106A" box="[996,1005,851,871]" italics="true" pageId="1" pageNumber="84">s</emphasis>
|
||
</geoCoordinate>
|
||
. Their
|
||
<superScript id="519A4E198B4BFFE9FBDAFCE9EB271051" attach="right" box="[1081,1090,848,860]" fontSize="5" pageId="1" pageNumber="84">1</superScript>
|
||
<collectionCode id="C0FE7B948B4BFFE9FBA1FCEDEB37106A" box="[1090,1106,852,871]" country="Finland" lsid="urn:lsid:biocol.org:col:15618" name="University of Helsinki" pageId="1" pageNumber="84" type="Herbarium">H</collectionCode>
|
||
and
|
||
<superScript id="519A4E198B4BFFE9FB68FCE9EBF81051" attach="right" box="[1163,1181,848,860]" fontSize="5" pageId="1" pageNumber="84">13</superScript>
|
||
<collectionCode id="C0FE7B948B4BFFE9FB7EFCEDEBCF106A" box="[1181,1194,852,871]" country="Denmark" name="University of Copenhagen" pageId="1" pageNumber="84" type="Herbarium">C</collectionCode>
|
||
<collectionCode id="C0FE7B948B4BFFE9FB57FCEDEB83106A" box="[1204,1254,852,871]" country="Netherlands" httpUri="http://grbio.org/cool/jyde-k516" name="Natuurhistorisch Museum" pageId="1" pageNumber="84">NMR</collectionCode>
|
||
spectra were closely related to those of compound
|
||
<emphasis id="949B3F438B4BFFE9FBB8FCC9EB0D108E" bold="true" box="[1115,1128,880,899]" pageId="1" pageNumber="84">1</emphasis>
|
||
, differing only in the substitution pattern of ring
|
||
<collectionCode id="C0FE7B948B4BFFE9FC21FC35ECB51092" box="[962,976,908,927]" country="USA" lsid="urn:lsid:biocol.org:col:15406" name="Harvard University - Arnold Arboretum" pageId="1" pageNumber="84" type="Herbarium">A</collectionCode>
|
||
(
|
||
<tableCitation id="EB6DD6EA8B4BFFE9FC03FC32EB511092" box="[992,1076,907,927]" captionStart="Table 1" captionStartId="2.[265,309,183,197]" captionTargetPageId="2" captionText="Table 1 1H NMR spectroscopic data of compounds 1–3 in CDCl. a 3" pageId="1" pageNumber="84">Tables 1</tableCitation>
|
||
and
|
||
<tableCitation id="EB6DD6EA8B4BFFE9FB8AFC35EB131092" box="[1129,1142,908,927]" captionStart="Table 3" captionStartId="4.[114,158,183,197]" captionTargetPageId="4" captionText="Table 3 13C NMR spectroscopic data of compounds 18 in CDCl. a 3" pageId="1" pageNumber="84">3</tableCitation>
|
||
).
|
||
<specimenCode id="F6494B2A8B4BFFE9FB69FC35EBCD1093" box="[1162,1192,907,927]" collectionCode="A" country="USA" lsid="urn:lsid:biocol.org:col:15406" name="Harvard University - Arnold Arboretum" pageId="1" pageNumber="84" type="Herbarium">A 1</specimenCode>
|
||
-oxo-3,5-diene-7
|
||
<emphasis id="949B3F438B4BFFE9FAB4FC35EA001092" bold="true" box="[1367,1381,908,927]" pageId="1" pageNumber="84">a</emphasis>
|
||
-hydroxy substitution pattern was inferred from the following observations: (i) two mutually coupled olefinic signals resonating at
|
||
<emphasis id="949B3F438B4BFFE9FABAFC7DEA0110DA" bold="true" box="[1369,1380,964,983]" italics="true" pageId="1" pageNumber="84">δ</emphasis>
|
||
5.81 (
|
||
<emphasis id="949B3F438B4BFFE9FA44FC7BEADF10DB" box="[1447,1466,962,982]" italics="true" pageId="1" pageNumber="84">m</emphasis>
|
||
) and 6.10 (
|
||
<emphasis id="949B3F438B4BFFE9FC6CFC67ECDD10FF" box="[911,952,990,1010]" italics="true" pageId="1" pageNumber="84">br d</emphasis>
|
||
,
|
||
<emphasis id="949B3F438B4BFFE9FC25FC67ECA810FF" box="[966,973,990,1010]" italics="true" pageId="1" pageNumber="84">
|
||
<collectionCode id="C0FE7B948B4BFFE9FC25FC67ECA810FF" box="[966,973,990,1010]" country="South Africa" lsid="urn:lsid:biocol.org:col:14647" name="University of the Witwatersrand" pageId="1" pageNumber="84" type="Herbarium">J</collectionCode>
|
||
</emphasis>
|
||
= 9.7 Hz) assigned to H-3 and H-4, respectively; (ii) the downfield shift of the carbonyl carbon in the
|
||
<superScript id="519A4E198B48FFEAFD51FB3BEDA01783" attach="right" box="[690,709,1154,1166]" fontSize="5" pageId="2" pageNumber="85">13</superScript>
|
||
C NMR spectrum from
|
||
<emphasis id="949B3F438B48FFEAFEF5FB1BEE4417B8" bold="true" box="[278,289,1186,1205]" italics="true" pageId="2" pageNumber="85">δ</emphasis>
|
||
203.0/203.3 for compound
|
||
<emphasis id="949B3F438B48FFEAFDA8FB18ED3D17B9" bold="true" box="[587,600,1185,1204]" pageId="2" pageNumber="85">1</emphasis>
|
||
to
|
||
<emphasis id="949B3F438B48FFEAFD61FB1BEDE817B8" bold="true" box="[642,653,1186,1205]" italics="true" pageId="2" pageNumber="85">δ</emphasis>
|
||
209.6/209.8 for compound
|
||
<emphasis id="949B3F438B48FFEAFEE8FB04EE7D17DD" bold="true" box="[267,280,1213,1232]" pageId="2" pageNumber="85">2</emphasis>
|
||
, assigned to C-1; (iii) the downfield shift of H
|
||
<quantity id="61174EB48B48FFEAFD1EFB7EEFC317E1" metricMagnitude="-1" metricUnit="m" metricValue="2.794" metricValueMax="4.826" metricValueMin="0.762" pageId="2" pageNumber="85" unit="in" value="11.0" valueMax="19.0" valueMin="3.0">
|
||
<subScript id="3A6BE1148B48FFEAFD1EFB7EEC6317DE" attach="right" box="[765,774,1223,1235]" fontSize="5" pageId="2" pageNumber="85">3</subScript>
|
||
- 19 in
|
||
</quantity>
|
||
the
|
||
<superScript id="519A4E198B48FFEAFF35FB6CEFBA17EC" attach="right" box="[214,223,1237,1249]" fontSize="5" pageId="2" pageNumber="85">1</superScript>
|
||
H NMR spectrum from
|
||
<emphasis id="949B3F438B48FFEAFE33FB63EEBE17E0" bold="true" box="[464,475,1242,1261]" italics="true" pageId="2" pageNumber="85">δ</emphasis>
|
||
1.21/1.23 for
|
||
<emphasis id="949B3F438B48FFEAFD8EFB60ED1F17E1" bold="true" box="[621,634,1241,1260]" pageId="2" pageNumber="85">1</emphasis>
|
||
to
|
||
<emphasis id="949B3F438B48FFEAFD7DFB63EDCC17E0" bold="true" box="[670,681,1242,1261]" italics="true" pageId="2" pageNumber="85">δ</emphasis>
|
||
1.32/1.34 for
|
||
<emphasis id="949B3F438B48FFEAFF75FB4CEFC61605" bold="true" box="[150,163,1269,1288]" pageId="2" pageNumber="85">2</emphasis>
|
||
. The
|
||
<superScript id="519A4E198B48FFEAFF3FFB48EF8A17F0" attach="right" box="[220,239,1265,1277]" fontSize="5" pageId="2" pageNumber="85">13</superScript>
|
||
C NMR signals corresponding to the A and B rings of withaphysalin W were in agreement with the proposed structure (
|
||
<bibRefCitation id="C27E9EA08B48FFEAFF99FA94EE54164D" author="Garcia, M. E. & Barboza, G. E. & Oberti, J. C. & Rios-Luci, C. & Padron, J. M. & Nicotra, V. E. & Estevez-Braun, A. & Ravelo, A. G." box="[122,305,1325,1344]" pageId="2" pageNumber="85" pagination="150 - 157" refId="ref8651" refString="Garcia, M. E., Barboza, G. E., Oberti, J. C., Rios-Luci, C., Padron, J. M., Nicotra, V. E., Estevez-Braun, A., Ravelo, A. G., 2012. Antiproliferative activity of withanolide derivatives from Jaborosa cabrerae and J. reflexa. Chemotaxonomical considerations. Phytochemistry 76, 150 - 157." type="journal article" year="2012">García et al., 2012</bibRefCitation>
|
||
).
|
||
</paragraph>
|
||
</subSubSection>
|
||
</treatment>
|
||
</document> |