Loading…

Stereoselective Total Synthesis of (−)-Spirofungin A by Utilising Hydrogen-Bond Controlled Spiroketalisation

The stereoselective total synthesis of the spiroketal containing Streptomyces metabolite (−)‐spirofungin A (1) is described. A key step involved a spiroketalisation controlled by an intramolecular H‐bond which favoured the desired spiroketal 4 (13:1 ratio). The presence of the intramolecular H‐bond...

Full description

Saved in:
Bibliographic Details
Published in:Chemistry : a European journal 2011-01, Vol.17 (1), p.297-304
Main Authors: Lynch, John E., Zanatta, Shannon D., White, Jonathan M., Rizzacasa, Mark A.
Format: Article
Language:English
Subjects:
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
cited_by cdi_FETCH-LOGICAL-c3821-daf21bb9c98c4c64bf1a6bfabb511918e3177298d10ce66423d06aef92bf95843
cites cdi_FETCH-LOGICAL-c3821-daf21bb9c98c4c64bf1a6bfabb511918e3177298d10ce66423d06aef92bf95843
container_end_page 304
container_issue 1
container_start_page 297
container_title Chemistry : a European journal
container_volume 17
creator Lynch, John E.
Zanatta, Shannon D.
White, Jonathan M.
Rizzacasa, Mark A.
description The stereoselective total synthesis of the spiroketal containing Streptomyces metabolite (−)‐spirofungin A (1) is described. A key step involved a spiroketalisation controlled by an intramolecular H‐bond which favoured the desired spiroketal 4 (13:1 ratio). The presence of the intramolecular H‐bond in 4 is possibly due to a 1,5‐alkyne–oxygen interaction. Other key steps include an efficient cross‐metathesis to form the spiroketal precursor, a tin mediated syn‐aldol reaction and a Stille cross‐coupling reaction to create the C22C23 bond. A final Wittig extension followed by deprotection gave (−)‐spirofungin A (1). Spiro key: The stereoselective total synthesis of the spiroketal‐containing Streptomyces metabolite (−)‐spirofungin A (1) is described. A key step involved a spiroketalisation controlled by an intramolecular hydrogen bond, which favoured the desired spiroketal 2 (13:1 ratio). Other key steps include an efficient cross‐metathesis to form the spiroketal precursor and a Stille cross‐coupling reaction. A final Wittig extension followed by deprotection gave 1.
doi_str_mv 10.1002/chem.201002501
format article
fullrecord <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_822708435</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>822708435</sourcerecordid><originalsourceid>FETCH-LOGICAL-c3821-daf21bb9c98c4c64bf1a6bfabb511918e3177298d10ce66423d06aef92bf95843</originalsourceid><addsrcrecordid>eNqFkL9vEzEYhi0EomlhZUTegOGCf5x957FEbYJUYEgr2Cyf73NqejkH24HexoLEzJ_Yv4QLKREb0_cOz_tI34vQM0qmlBD22l7DesrILgtCH6AJFYwWvJLiIZoQVVaFFFwdoeOUPhNClOT8MTpilJFKMjFBm2WGCCFBBzb7r4AvQzYdXg59vobkEw4Ov7z7-etVsdz4GNy2X_n-7vuPU9wM-Cr7ziffr_BiaGNYQV-8CX2LZ6HPMXQdtPhP6wZGp08m-9A_QY-c6RI8vb8n6Or87HK2KC4-zN_OTi8Ky-vxg9Y4RptGWVXb0sqycdTIxpmmEZQqWgOnVcVU3VJiQcqS8ZZIA06xxilRl_wEvdh7NzF82ULKeu2Tha4zPYRt0jVjFRk5MZLTPWljSCmC05vo1yYOmhK9G1bvRtaHkcfC83v1tllDe8D_rjoCag988x0M_9Hp2eLs3b_yYt_1KcPtoWvijZYVr4T--H6u5-TT-ZgrTfhvlz-bDw</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>822708435</pqid></control><display><type>article</type><title>Stereoselective Total Synthesis of (−)-Spirofungin A by Utilising Hydrogen-Bond Controlled Spiroketalisation</title><source>Wiley-Blackwell Read &amp; Publish Collection</source><creator>Lynch, John E. ; Zanatta, Shannon D. ; White, Jonathan M. ; Rizzacasa, Mark A.</creator><creatorcontrib>Lynch, John E. ; Zanatta, Shannon D. ; White, Jonathan M. ; Rizzacasa, Mark A.</creatorcontrib><description>The stereoselective total synthesis of the spiroketal containing Streptomyces metabolite (−)‐spirofungin A (1) is described. A key step involved a spiroketalisation controlled by an intramolecular H‐bond which favoured the desired spiroketal 4 (13:1 ratio). The presence of the intramolecular H‐bond in 4 is possibly due to a 1,5‐alkyne–oxygen interaction. Other key steps include an efficient cross‐metathesis to form the spiroketal precursor, a tin mediated syn‐aldol reaction and a Stille cross‐coupling reaction to create the C22C23 bond. A final Wittig extension followed by deprotection gave (−)‐spirofungin A (1). Spiro key: The stereoselective total synthesis of the spiroketal‐containing Streptomyces metabolite (−)‐spirofungin A (1) is described. A key step involved a spiroketalisation controlled by an intramolecular hydrogen bond, which favoured the desired spiroketal 2 (13:1 ratio). Other key steps include an efficient cross‐metathesis to form the spiroketal precursor and a Stille cross‐coupling reaction. A final Wittig extension followed by deprotection gave 1.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.201002501</identifier><identifier>PMID: 21207625</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>Furans - chemical synthesis ; Furans - chemistry ; Hydrogen Bonding ; hydrogen bonds ; Molecular Structure ; natural products ; Pyrans - chemical synthesis ; Pyrans - chemistry ; Spiro Compounds - chemical synthesis ; Spiro Compounds - chemistry ; spirofungins ; spiroketals ; Stereoisomerism ; Streptomyces - chemistry ; total synthesis</subject><ispartof>Chemistry : a European journal, 2011-01, Vol.17 (1), p.297-304</ispartof><rights>Copyright © 2011 WILEY‐VCH Verlag GmbH &amp; Co. KGaA, Weinheim</rights><rights>Copyright © 2011 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3821-daf21bb9c98c4c64bf1a6bfabb511918e3177298d10ce66423d06aef92bf95843</citedby><cites>FETCH-LOGICAL-c3821-daf21bb9c98c4c64bf1a6bfabb511918e3177298d10ce66423d06aef92bf95843</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27903,27904</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/21207625$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Lynch, John E.</creatorcontrib><creatorcontrib>Zanatta, Shannon D.</creatorcontrib><creatorcontrib>White, Jonathan M.</creatorcontrib><creatorcontrib>Rizzacasa, Mark A.</creatorcontrib><title>Stereoselective Total Synthesis of (−)-Spirofungin A by Utilising Hydrogen-Bond Controlled Spiroketalisation</title><title>Chemistry : a European journal</title><addtitle>Chem. Eur. J</addtitle><description>The stereoselective total synthesis of the spiroketal containing Streptomyces metabolite (−)‐spirofungin A (1) is described. A key step involved a spiroketalisation controlled by an intramolecular H‐bond which favoured the desired spiroketal 4 (13:1 ratio). The presence of the intramolecular H‐bond in 4 is possibly due to a 1,5‐alkyne–oxygen interaction. Other key steps include an efficient cross‐metathesis to form the spiroketal precursor, a tin mediated syn‐aldol reaction and a Stille cross‐coupling reaction to create the C22C23 bond. A final Wittig extension followed by deprotection gave (−)‐spirofungin A (1). Spiro key: The stereoselective total synthesis of the spiroketal‐containing Streptomyces metabolite (−)‐spirofungin A (1) is described. A key step involved a spiroketalisation controlled by an intramolecular hydrogen bond, which favoured the desired spiroketal 2 (13:1 ratio). Other key steps include an efficient cross‐metathesis to form the spiroketal precursor and a Stille cross‐coupling reaction. A final Wittig extension followed by deprotection gave 1.</description><subject>Furans - chemical synthesis</subject><subject>Furans - chemistry</subject><subject>Hydrogen Bonding</subject><subject>hydrogen bonds</subject><subject>Molecular Structure</subject><subject>natural products</subject><subject>Pyrans - chemical synthesis</subject><subject>Pyrans - chemistry</subject><subject>Spiro Compounds - chemical synthesis</subject><subject>Spiro Compounds - chemistry</subject><subject>spirofungins</subject><subject>spiroketals</subject><subject>Stereoisomerism</subject><subject>Streptomyces - chemistry</subject><subject>total synthesis</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2011</creationdate><recordtype>article</recordtype><recordid>eNqFkL9vEzEYhi0EomlhZUTegOGCf5x957FEbYJUYEgr2Cyf73NqejkH24HexoLEzJ_Yv4QLKREb0_cOz_tI34vQM0qmlBD22l7DesrILgtCH6AJFYwWvJLiIZoQVVaFFFwdoeOUPhNClOT8MTpilJFKMjFBm2WGCCFBBzb7r4AvQzYdXg59vobkEw4Ov7z7-etVsdz4GNy2X_n-7vuPU9wM-Cr7ziffr_BiaGNYQV-8CX2LZ6HPMXQdtPhP6wZGp08m-9A_QY-c6RI8vb8n6Or87HK2KC4-zN_OTi8Ky-vxg9Y4RptGWVXb0sqycdTIxpmmEZQqWgOnVcVU3VJiQcqS8ZZIA06xxilRl_wEvdh7NzF82ULKeu2Tha4zPYRt0jVjFRk5MZLTPWljSCmC05vo1yYOmhK9G1bvRtaHkcfC83v1tllDe8D_rjoCag988x0M_9Hp2eLs3b_yYt_1KcPtoWvijZYVr4T--H6u5-TT-ZgrTfhvlz-bDw</recordid><startdate>20110103</startdate><enddate>20110103</enddate><creator>Lynch, John E.</creator><creator>Zanatta, Shannon D.</creator><creator>White, Jonathan M.</creator><creator>Rizzacasa, Mark A.</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><scope>BSCLL</scope><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></search><sort><creationdate>20110103</creationdate><title>Stereoselective Total Synthesis of (−)-Spirofungin A by Utilising Hydrogen-Bond Controlled Spiroketalisation</title><author>Lynch, John E. ; Zanatta, Shannon D. ; White, Jonathan M. ; Rizzacasa, Mark A.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3821-daf21bb9c98c4c64bf1a6bfabb511918e3177298d10ce66423d06aef92bf95843</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2011</creationdate><topic>Furans - chemical synthesis</topic><topic>Furans - chemistry</topic><topic>Hydrogen Bonding</topic><topic>hydrogen bonds</topic><topic>Molecular Structure</topic><topic>natural products</topic><topic>Pyrans - chemical synthesis</topic><topic>Pyrans - chemistry</topic><topic>Spiro Compounds - chemical synthesis</topic><topic>Spiro Compounds - chemistry</topic><topic>spirofungins</topic><topic>spiroketals</topic><topic>Stereoisomerism</topic><topic>Streptomyces - chemistry</topic><topic>total synthesis</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Lynch, John E.</creatorcontrib><creatorcontrib>Zanatta, Shannon D.</creatorcontrib><creatorcontrib>White, Jonathan M.</creatorcontrib><creatorcontrib>Rizzacasa, Mark A.</creatorcontrib><collection>Istex</collection><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><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Lynch, John E.</au><au>Zanatta, Shannon D.</au><au>White, Jonathan M.</au><au>Rizzacasa, Mark A.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Stereoselective Total Synthesis of (−)-Spirofungin A by Utilising Hydrogen-Bond Controlled Spiroketalisation</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chem. Eur. J</addtitle><date>2011-01-03</date><risdate>2011</risdate><volume>17</volume><issue>1</issue><spage>297</spage><epage>304</epage><pages>297-304</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>The stereoselective total synthesis of the spiroketal containing Streptomyces metabolite (−)‐spirofungin A (1) is described. A key step involved a spiroketalisation controlled by an intramolecular H‐bond which favoured the desired spiroketal 4 (13:1 ratio). The presence of the intramolecular H‐bond in 4 is possibly due to a 1,5‐alkyne–oxygen interaction. Other key steps include an efficient cross‐metathesis to form the spiroketal precursor, a tin mediated syn‐aldol reaction and a Stille cross‐coupling reaction to create the C22C23 bond. A final Wittig extension followed by deprotection gave (−)‐spirofungin A (1). Spiro key: The stereoselective total synthesis of the spiroketal‐containing Streptomyces metabolite (−)‐spirofungin A (1) is described. A key step involved a spiroketalisation controlled by an intramolecular hydrogen bond, which favoured the desired spiroketal 2 (13:1 ratio). Other key steps include an efficient cross‐metathesis to form the spiroketal precursor and a Stille cross‐coupling reaction. A final Wittig extension followed by deprotection gave 1.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>21207625</pmid><doi>10.1002/chem.201002501</doi><tpages>8</tpages></addata></record>
fulltext fulltext
identifier ISSN: 0947-6539
ispartof Chemistry : a European journal, 2011-01, Vol.17 (1), p.297-304
issn 0947-6539
1521-3765
language eng
recordid cdi_proquest_miscellaneous_822708435
source Wiley-Blackwell Read & Publish Collection
subjects Furans - chemical synthesis
Furans - chemistry
Hydrogen Bonding
hydrogen bonds
Molecular Structure
natural products
Pyrans - chemical synthesis
Pyrans - chemistry
Spiro Compounds - chemical synthesis
Spiro Compounds - chemistry
spirofungins
spiroketals
Stereoisomerism
Streptomyces - chemistry
total synthesis
title Stereoselective Total Synthesis of (−)-Spirofungin A by Utilising Hydrogen-Bond Controlled Spiroketalisation
url http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-26T08%3A49%3A36IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Stereoselective%20Total%20Synthesis%20of%20(%E2%88%92)-Spirofungin%E2%80%85A%20by%20Utilising%20Hydrogen-Bond%20Controlled%20Spiroketalisation&rft.jtitle=Chemistry%20:%20a%20European%20journal&rft.au=Lynch,%20John%20E.&rft.date=2011-01-03&rft.volume=17&rft.issue=1&rft.spage=297&rft.epage=304&rft.pages=297-304&rft.issn=0947-6539&rft.eissn=1521-3765&rft_id=info:doi/10.1002/chem.201002501&rft_dat=%3Cproquest_cross%3E822708435%3C/proquest_cross%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-c3821-daf21bb9c98c4c64bf1a6bfabb511918e3177298d10ce66423d06aef92bf95843%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_pqid=822708435&rft_id=info:pmid/21207625&rfr_iscdi=true