Stereocontrolled Synthesis of 1,5-Stereogenic Centers through Three-Carbon Homologation of Boronic Esters
Allylic pinacol boronic esters are stable toward 1,3‐borotropic rearrangement. We developed a PdII‐mediated isomerization process that gives di‐ or trisubstituted allylic boronic esters with high E selectivity. The combination of this method with lithiation–borylation enables the synthesis of carbon...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2014-09, Vol.53 (37), p.9846-9850 |
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| creator | Unsworth, Phillip J. Leonori, Daniele Aggarwal, Varinder K. |
| description | Allylic pinacol boronic esters are stable toward 1,3‐borotropic rearrangement. We developed a PdII‐mediated isomerization process that gives di‐ or trisubstituted allylic boronic esters with high E selectivity. The combination of this method with lithiation–borylation enables the synthesis of carbon chains that bear 1,5‐stereogenic centers. The utility of this method has been demonstrated in a formal synthesis of (+)‐jasplakinolide.
Three more: The 3C homologation of chiral pinacol boronic esters gives di‐ or trisubstituted allylic boronic esters with high yield and E selectivities. The combination of this method with lithiation–borylation enables the synthesis of alkyl chains that bear 1,5‐stereogenic centers. The utility of the process was demonstrated in a formal synthesis of (+)‐jasplakinolide. |
| doi_str_mv | 10.1002/anie.201405700 |
| format | Article |
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Three more: The 3C homologation of chiral pinacol boronic esters gives di‐ or trisubstituted allylic boronic esters with high yield and E selectivities. The combination of this method with lithiation–borylation enables the synthesis of alkyl chains that bear 1,5‐stereogenic centers. The utility of the process was demonstrated in a formal synthesis of (+)‐jasplakinolide.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201405700</identifier><identifier>PMID: 25044518</identifier><identifier>CODEN: ACIEAY</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>1,5‐stereocenters ; 5-stereocenters ; allylic boronic esters ; asymmetric synthesis ; Boronic Acids - chemical synthesis ; Boronic Acids - chemistry ; Carbon ; Catalysis ; Esters ; Esters - chemical synthesis ; Esters - chemistry ; Homology ; Isomerization ; lithiation-borylation ; Molecular Structure ; palladium ; Stereoisomerism ; Synthesis ; Utilities</subject><ispartof>Angewandte Chemie International Edition, 2014-09, Vol.53 (37), p.9846-9850</ispartof><rights>2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5470-3148bdd8eee41878688a9397d215cbcb4b365bdf2588d28de4dab1ebd5033f673</citedby><cites>FETCH-LOGICAL-c5470-3148bdd8eee41878688a9397d215cbcb4b365bdf2588d28de4dab1ebd5033f673</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.201405700$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201405700$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/25044518$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Unsworth, Phillip J.</creatorcontrib><creatorcontrib>Leonori, Daniele</creatorcontrib><creatorcontrib>Aggarwal, Varinder K.</creatorcontrib><title>Stereocontrolled Synthesis of 1,5-Stereogenic Centers through Three-Carbon Homologation of Boronic Esters</title><title>Angewandte Chemie International Edition</title><addtitle>Angew. Chem. Int. Ed</addtitle><description>Allylic pinacol boronic esters are stable toward 1,3‐borotropic rearrangement. We developed a PdII‐mediated isomerization process that gives di‐ or trisubstituted allylic boronic esters with high E selectivity. The combination of this method with lithiation–borylation enables the synthesis of carbon chains that bear 1,5‐stereogenic centers. The utility of this method has been demonstrated in a formal synthesis of (+)‐jasplakinolide.
Three more: The 3C homologation of chiral pinacol boronic esters gives di‐ or trisubstituted allylic boronic esters with high yield and E selectivities. The combination of this method with lithiation–borylation enables the synthesis of alkyl chains that bear 1,5‐stereogenic centers. The utility of the process was demonstrated in a formal synthesis of (+)‐jasplakinolide.</description><subject>1,5‐stereocenters</subject><subject>5-stereocenters</subject><subject>allylic boronic esters</subject><subject>asymmetric synthesis</subject><subject>Boronic Acids - chemical synthesis</subject><subject>Boronic Acids - chemistry</subject><subject>Carbon</subject><subject>Catalysis</subject><subject>Esters</subject><subject>Esters - chemical synthesis</subject><subject>Esters - chemistry</subject><subject>Homology</subject><subject>Isomerization</subject><subject>lithiation-borylation</subject><subject>Molecular Structure</subject><subject>palladium</subject><subject>Stereoisomerism</subject><subject>Synthesis</subject><subject>Utilities</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkU1v1DAURS0Eoh-wZYkisWFBhufYjp1lOxraSlUBtVCJjeXELzMumbjYicr8exyljBCbruwnnXPl50vIGwoLClB8NL3DRQGUg5AAz8ghFQXNmZTsebpzxnKpBD0gRzHeJV4pKF-Sg0IA54KqQ-KuBwzoG98PwXcd2ux61w8bjC5mvs3oB5HPxBp712RL7NMUs2ET_LjeZDebgJgvTah9n537re_82gwuDUk-9cFP0ipOzivyojVdxNeP5zH59ml1szzPLz-fXSxPLvNGcAk5o1zV1ipE5FRJVSplKlZJW1DR1E3Na1aK2raFUMoWyiK3pqZYWwGMtaVkx-T9nHsf_K8R46C3LjbYdaZHP0ZNJVAoS57wJ1FRAlSlBJHQd_-hd34MfVokUekpUBVyohYz1QQfY8BW3we3NWGnKeipLz31pfd9JeHtY-xYb9Hu8b8FJaCagQfX4e6JOH1ydbH6NzyfXZcK-L13Tfip0z9JoW-vzvSP2-9fBYMv-pT9AcFtsHA</recordid><startdate>20140908</startdate><enddate>20140908</enddate><creator>Unsworth, Phillip J.</creator><creator>Leonori, Daniele</creator><creator>Aggarwal, Varinder K.</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><general>Wiley Subscription Services, Inc</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>7TM</scope><scope>K9.</scope><scope>7X8</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>20140908</creationdate><title>Stereocontrolled Synthesis of 1,5-Stereogenic Centers through Three-Carbon Homologation of Boronic Esters</title><author>Unsworth, Phillip J. ; Leonori, Daniele ; Aggarwal, Varinder K.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5470-3148bdd8eee41878688a9397d215cbcb4b365bdf2588d28de4dab1ebd5033f673</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>1,5‐stereocenters</topic><topic>5-stereocenters</topic><topic>allylic boronic esters</topic><topic>asymmetric synthesis</topic><topic>Boronic Acids - chemical synthesis</topic><topic>Boronic Acids - chemistry</topic><topic>Carbon</topic><topic>Catalysis</topic><topic>Esters</topic><topic>Esters - chemical synthesis</topic><topic>Esters - chemistry</topic><topic>Homology</topic><topic>Isomerization</topic><topic>lithiation-borylation</topic><topic>Molecular Structure</topic><topic>palladium</topic><topic>Stereoisomerism</topic><topic>Synthesis</topic><topic>Utilities</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Unsworth, Phillip J.</creatorcontrib><creatorcontrib>Leonori, Daniele</creatorcontrib><creatorcontrib>Aggarwal, Varinder K.</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>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Unsworth, Phillip J.</au><au>Leonori, Daniele</au><au>Aggarwal, Varinder K.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Stereocontrolled Synthesis of 1,5-Stereogenic Centers through Three-Carbon Homologation of Boronic Esters</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew. Chem. Int. Ed</addtitle><date>2014-09-08</date><risdate>2014</risdate><volume>53</volume><issue>37</issue><spage>9846</spage><epage>9850</epage><pages>9846-9850</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><coden>ACIEAY</coden><abstract>Allylic pinacol boronic esters are stable toward 1,3‐borotropic rearrangement. We developed a PdII‐mediated isomerization process that gives di‐ or trisubstituted allylic boronic esters with high E selectivity. The combination of this method with lithiation–borylation enables the synthesis of carbon chains that bear 1,5‐stereogenic centers. The utility of this method has been demonstrated in a formal synthesis of (+)‐jasplakinolide.
Three more: The 3C homologation of chiral pinacol boronic esters gives di‐ or trisubstituted allylic boronic esters with high yield and E selectivities. The combination of this method with lithiation–borylation enables the synthesis of alkyl chains that bear 1,5‐stereogenic centers. The utility of the process was demonstrated in a formal synthesis of (+)‐jasplakinolide.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>25044518</pmid><doi>10.1002/anie.201405700</doi><tpages>5</tpages><edition>International ed. in English</edition></addata></record> |
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| source | MEDLINE; Wiley Online Library All Journals |
| subjects | 1,5‐stereocenters 5-stereocenters allylic boronic esters asymmetric synthesis Boronic Acids - chemical synthesis Boronic Acids - chemistry Carbon Catalysis Esters Esters - chemical synthesis Esters - chemistry Homology Isomerization lithiation-borylation Molecular Structure palladium Stereoisomerism Synthesis Utilities |
| title | Stereocontrolled Synthesis of 1,5-Stereogenic Centers through Three-Carbon Homologation of Boronic Esters |
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