Absolute Configuration of Isosilybin A by X‑ray Crystallography of the Heavy Atom Analogue 7‑(4-Bromobenzoyl)isosilybin A
Isosilybin A (1) is one of the major flavonolignans that constitute silymarin, an extract of the fruits (achenes) of milk thistle (Silybum marianum). The chemistry of the Silybum flavonolignans has been studied for over four decades, and the absolute configuration of 1 has been determined previously...
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| Veröffentlicht in: | Journal of natural products (Washington, D.C.) D.C.), 2012-11, Vol.75 (11), p.1879-1881 |
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| container_end_page | 1881 |
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| container_issue | 11 |
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| container_title | Journal of natural products (Washington, D.C.) |
| container_volume | 75 |
| creator | Sy-Cordero, Arlene A Day, Cynthia S Oberlies, Nicholas H |
| description | Isosilybin A (1) is one of the major flavonolignans that constitute silymarin, an extract of the fruits (achenes) of milk thistle (Silybum marianum). The chemistry of the Silybum flavonolignans has been studied for over four decades, and the absolute configuration of 1 has been determined previously by electronic circular dichroism and X-ray crystallography via correlating the relative configuration of the phenylpropanoid moiety to the established absolute configuration of the 3-hydroxyflavanone portion of the molecule. Herein we report the X-ray crystallographic structure of the product of the reaction of 1 with 4-bromobenzoyl chloride, and, thus, the absolute configuration of 1 was established as (2R, 3R, 7″R, 8″R) directly via X-ray crystallography of an analogue that incorporated a heavy atom. The results were consistent with previously reported assignments and verified the absolute configuration of the diastereoisomer of 1, isosilybin B, and the related diastereoisomeric regioisomers, silybin A and silybin B. |
| doi_str_mv | 10.1021/np3005369 |
| format | Article |
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The chemistry of the Silybum flavonolignans has been studied for over four decades, and the absolute configuration of 1 has been determined previously by electronic circular dichroism and X-ray crystallography via correlating the relative configuration of the phenylpropanoid moiety to the established absolute configuration of the 3-hydroxyflavanone portion of the molecule. Herein we report the X-ray crystallographic structure of the product of the reaction of 1 with 4-bromobenzoyl chloride, and, thus, the absolute configuration of 1 was established as (2R, 3R, 7″R, 8″R) directly via X-ray crystallography of an analogue that incorporated a heavy atom. The results were consistent with previously reported assignments and verified the absolute configuration of the diastereoisomer of 1, isosilybin B, and the related diastereoisomeric regioisomers, silybin A and silybin B.</description><identifier>ISSN: 0163-3864</identifier><identifier>ISSN: 1520-6025</identifier><identifier>EISSN: 1520-6025</identifier><identifier>DOI: 10.1021/np3005369</identifier><identifier>PMID: 23116206</identifier><language>eng</language><publisher>United States: American Chemical Society and American Society of Pharmacognosy</publisher><subject>chemical structure ; chlorides ; Circular Dichroism ; circular dichroism spectroscopy ; Crystallography, X-Ray ; Flavanones - chemistry ; Flavonolignans - chemistry ; Fruit ; fruits ; Molecular Conformation ; Molecular Structure ; Silybin ; Silybum marianum ; Silybum marianum - chemistry ; silymarin ; Silymarin - analogs & derivatives ; Silymarin - chemistry ; Stereoisomerism ; X-ray diffraction</subject><ispartof>Journal of natural products (Washington, D.C.), 2012-11, Vol.75 (11), p.1879-1881</ispartof><rights>Copyright © 2012 American Chemical Society and American Society of Pharmacognosy</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a471t-6fcc7f81578e4d8cae9d5da5721be223e722632a9efb272b5ea79c95eb81945f3</citedby><cites>FETCH-LOGICAL-a471t-6fcc7f81578e4d8cae9d5da5721be223e722632a9efb272b5ea79c95eb81945f3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/np3005369$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/np3005369$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,776,780,881,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/23116206$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Sy-Cordero, Arlene A</creatorcontrib><creatorcontrib>Day, Cynthia S</creatorcontrib><creatorcontrib>Oberlies, Nicholas H</creatorcontrib><title>Absolute Configuration of Isosilybin A by X‑ray Crystallography of the Heavy Atom Analogue 7‑(4-Bromobenzoyl)isosilybin A</title><title>Journal of natural products (Washington, D.C.)</title><addtitle>J. Nat. Prod</addtitle><description>Isosilybin A (1) is one of the major flavonolignans that constitute silymarin, an extract of the fruits (achenes) of milk thistle (Silybum marianum). The chemistry of the Silybum flavonolignans has been studied for over four decades, and the absolute configuration of 1 has been determined previously by electronic circular dichroism and X-ray crystallography via correlating the relative configuration of the phenylpropanoid moiety to the established absolute configuration of the 3-hydroxyflavanone portion of the molecule. Herein we report the X-ray crystallographic structure of the product of the reaction of 1 with 4-bromobenzoyl chloride, and, thus, the absolute configuration of 1 was established as (2R, 3R, 7″R, 8″R) directly via X-ray crystallography of an analogue that incorporated a heavy atom. The results were consistent with previously reported assignments and verified the absolute configuration of the diastereoisomer of 1, isosilybin B, and the related diastereoisomeric regioisomers, silybin A and silybin B.</description><subject>chemical structure</subject><subject>chlorides</subject><subject>Circular Dichroism</subject><subject>circular dichroism spectroscopy</subject><subject>Crystallography, X-Ray</subject><subject>Flavanones - chemistry</subject><subject>Flavonolignans - chemistry</subject><subject>Fruit</subject><subject>fruits</subject><subject>Molecular Conformation</subject><subject>Molecular Structure</subject><subject>Silybin</subject><subject>Silybum marianum</subject><subject>Silybum marianum - chemistry</subject><subject>silymarin</subject><subject>Silymarin - analogs & derivatives</subject><subject>Silymarin - chemistry</subject><subject>Stereoisomerism</subject><subject>X-ray diffraction</subject><issn>0163-3864</issn><issn>1520-6025</issn><issn>1520-6025</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2012</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFks1q3DAURkVpaKZpF32Bok0hWTjVj2Vbm4IztE0g0E0L3QnJcz2jIEtTyQ64UOgr9BXzJFGYZEigkIXQ4h4dSfe7CL2j5JQSRj_6LSdE8Eq-QAsqGCkqwsRLtCC04gVvqvIQvU7pihDCiRSv0CHjlFaMVAv0pzUpuGkEvAy-t-sp6tEGj0OPL1JI1s3GetxiM-OfN3__RT3jZZzTqJ0L66i3m_kOHTeAz0Ffz7gdw4Bbr3N1AlznI8dlcRbDEAz432F2J_aR9g066LVL8PZ-P0I_vnz-vjwvLr99vVi2l4UuazoWVd91dd9QUTdQrppOg1yJlRY1owYY41AzVnGmJfSG1cwI0LXspADTUFmKnh-hTzvvdjIDrDrwY9RObaMddJxV0FY9rXi7UetwrXjuUr4lC47vBTH8miCNarCpA-e0hzAlxXJvy5JK0jyL0lJKSkVO7HmUi6pp8uIZPdmhXQwpRej3j6dE3Q2B2g9BZt8__u2efEg9Ax92gO6SugpTzHml_4huAVhfuyg</recordid><startdate>20121126</startdate><enddate>20121126</enddate><creator>Sy-Cordero, Arlene A</creator><creator>Day, Cynthia S</creator><creator>Oberlies, Nicholas H</creator><general>American Chemical Society and American Society of Pharmacognosy</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7S9</scope><scope>L.6</scope><scope>5PM</scope></search><sort><creationdate>20121126</creationdate><title>Absolute Configuration of Isosilybin A by X‑ray Crystallography of the Heavy Atom Analogue 7‑(4-Bromobenzoyl)isosilybin A</title><author>Sy-Cordero, Arlene A ; Day, Cynthia S ; Oberlies, Nicholas H</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a471t-6fcc7f81578e4d8cae9d5da5721be223e722632a9efb272b5ea79c95eb81945f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2012</creationdate><topic>chemical structure</topic><topic>chlorides</topic><topic>Circular Dichroism</topic><topic>circular dichroism spectroscopy</topic><topic>Crystallography, X-Ray</topic><topic>Flavanones - chemistry</topic><topic>Flavonolignans - chemistry</topic><topic>Fruit</topic><topic>fruits</topic><topic>Molecular Conformation</topic><topic>Molecular Structure</topic><topic>Silybin</topic><topic>Silybum marianum</topic><topic>Silybum marianum - chemistry</topic><topic>silymarin</topic><topic>Silymarin - analogs & derivatives</topic><topic>Silymarin - chemistry</topic><topic>Stereoisomerism</topic><topic>X-ray diffraction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Sy-Cordero, Arlene A</creatorcontrib><creatorcontrib>Day, Cynthia S</creatorcontrib><creatorcontrib>Oberlies, Nicholas H</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>AGRICOLA</collection><collection>AGRICOLA - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Journal of natural products (Washington, D.C.)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Sy-Cordero, Arlene A</au><au>Day, Cynthia S</au><au>Oberlies, Nicholas H</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Absolute Configuration of Isosilybin A by X‑ray Crystallography of the Heavy Atom Analogue 7‑(4-Bromobenzoyl)isosilybin A</atitle><jtitle>Journal of natural products (Washington, D.C.)</jtitle><addtitle>J. Nat. Prod</addtitle><date>2012-11-26</date><risdate>2012</risdate><volume>75</volume><issue>11</issue><spage>1879</spage><epage>1881</epage><pages>1879-1881</pages><issn>0163-3864</issn><issn>1520-6025</issn><eissn>1520-6025</eissn><abstract>Isosilybin A (1) is one of the major flavonolignans that constitute silymarin, an extract of the fruits (achenes) of milk thistle (Silybum marianum). The chemistry of the Silybum flavonolignans has been studied for over four decades, and the absolute configuration of 1 has been determined previously by electronic circular dichroism and X-ray crystallography via correlating the relative configuration of the phenylpropanoid moiety to the established absolute configuration of the 3-hydroxyflavanone portion of the molecule. Herein we report the X-ray crystallographic structure of the product of the reaction of 1 with 4-bromobenzoyl chloride, and, thus, the absolute configuration of 1 was established as (2R, 3R, 7″R, 8″R) directly via X-ray crystallography of an analogue that incorporated a heavy atom. The results were consistent with previously reported assignments and verified the absolute configuration of the diastereoisomer of 1, isosilybin B, and the related diastereoisomeric regioisomers, silybin A and silybin B.</abstract><cop>United States</cop><pub>American Chemical Society and American Society of Pharmacognosy</pub><pmid>23116206</pmid><doi>10.1021/np3005369</doi><tpages>3</tpages><oa>free_for_read</oa></addata></record> |
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| language | eng |
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| source | MEDLINE; American Chemical Society Journals |
| subjects | chemical structure chlorides Circular Dichroism circular dichroism spectroscopy Crystallography, X-Ray Flavanones - chemistry Flavonolignans - chemistry Fruit fruits Molecular Conformation Molecular Structure Silybin Silybum marianum Silybum marianum - chemistry silymarin Silymarin - analogs & derivatives Silymarin - chemistry Stereoisomerism X-ray diffraction |
| title | Absolute Configuration of Isosilybin A by X‑ray Crystallography of the Heavy Atom Analogue 7‑(4-Bromobenzoyl)isosilybin A |
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