Gold(I)-Catalyzed Highly Diastereo- and Enantioselective Alkyne Oxidation/Cyclopropanation of 1,6-Enynes
A highly enantioselective oxidative cyclopropanation of 1,6‐enynes catalyzed by cationic AuI/chiral phophoramidite complexes is presented. The new method provides convenient access to densely functionalized bicyclo[3.1.0]hexanes bearing three contiguous quaternary and tertiary stereogenic centers wi...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2014-12, Vol.53 (50), p.13751-13755 |
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| creator | Qian, Deyun Hu, Haoxiang Liu, Feng Tang, Bin Ye, Weimin Wang, Yidong Zhang, Junliang |
| description | A highly enantioselective oxidative cyclopropanation of 1,6‐enynes catalyzed by cationic AuI/chiral phophoramidite complexes is presented. The new method provides convenient access to densely functionalized bicyclo[3.1.0]hexanes bearing three contiguous quaternary and tertiary stereogenic centers with high enantioselectivity (up to e.r. 98:2). Control experiments suggest that the quinoline moiety of the β‐gold vinyloxyquinolinium intermediate in the reaction plays an important role in promoting good enantioselectivity through a transitional auxiliary effect in the transition state.
Playing it safe: A highly enantioselective oxidative cyclopropanation of 1,6‐enynes with cationic AuI/chiral phosphoramidite catalysts provided convenient access to densely functionalized bicyclo[3.1.0]hexanes with three contiguous quaternary and tertiary stereogenic centers (see scheme; up to 92 % yield, e.r. 98:2). Control experiments suggest that the quinoline moiety in the oxidant plays an essential role in the enantioselective cyclopropanation. |
| doi_str_mv | 10.1002/anie.201407717 |
| format | Article |
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Playing it safe: A highly enantioselective oxidative cyclopropanation of 1,6‐enynes with cationic AuI/chiral phosphoramidite catalysts provided convenient access to densely functionalized bicyclo[3.1.0]hexanes with three contiguous quaternary and tertiary stereogenic centers (see scheme; up to 92 % yield, e.r. 98:2). Control experiments suggest that the quinoline moiety in the oxidant plays an essential role in the enantioselective cyclopropanation.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201407717</identifier><identifier>PMID: 25256143</identifier><identifier>CODEN: ACIEAY</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>alkyne oxidation ; Alkynes ; Bearing ; carbenoids ; Catalysis ; Catalysts ; Cationic ; cyclopropanation ; enantioselectivity ; gold ; Oxidants ; Oxidation ; Oxidizing agents ; Quinoline</subject><ispartof>Angewandte Chemie International Edition, 2014-12, Vol.53 (50), p.13751-13755</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-c4777-96c00e21985a4e2b4e0f3a2245d84ce5740a6df75238de1dad42f313b450d30c3</citedby><cites>FETCH-LOGICAL-c4777-96c00e21985a4e2b4e0f3a2245d84ce5740a6df75238de1dad42f313b450d30c3</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.201407717$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201407717$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27903,27904,45553,45554</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/25256143$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Qian, Deyun</creatorcontrib><creatorcontrib>Hu, Haoxiang</creatorcontrib><creatorcontrib>Liu, Feng</creatorcontrib><creatorcontrib>Tang, Bin</creatorcontrib><creatorcontrib>Ye, Weimin</creatorcontrib><creatorcontrib>Wang, Yidong</creatorcontrib><creatorcontrib>Zhang, Junliang</creatorcontrib><title>Gold(I)-Catalyzed Highly Diastereo- and Enantioselective Alkyne Oxidation/Cyclopropanation of 1,6-Enynes</title><title>Angewandte Chemie International Edition</title><addtitle>Angew. Chem. Int. Ed</addtitle><description>A highly enantioselective oxidative cyclopropanation of 1,6‐enynes catalyzed by cationic AuI/chiral phophoramidite complexes is presented. The new method provides convenient access to densely functionalized bicyclo[3.1.0]hexanes bearing three contiguous quaternary and tertiary stereogenic centers with high enantioselectivity (up to e.r. 98:2). Control experiments suggest that the quinoline moiety of the β‐gold vinyloxyquinolinium intermediate in the reaction plays an important role in promoting good enantioselectivity through a transitional auxiliary effect in the transition state.
Playing it safe: A highly enantioselective oxidative cyclopropanation of 1,6‐enynes with cationic AuI/chiral phosphoramidite catalysts provided convenient access to densely functionalized bicyclo[3.1.0]hexanes with three contiguous quaternary and tertiary stereogenic centers (see scheme; up to 92 % yield, e.r. 98:2). Control experiments suggest that the quinoline moiety in the oxidant plays an essential role in the enantioselective cyclopropanation.</description><subject>alkyne oxidation</subject><subject>Alkynes</subject><subject>Bearing</subject><subject>carbenoids</subject><subject>Catalysis</subject><subject>Catalysts</subject><subject>Cationic</subject><subject>cyclopropanation</subject><subject>enantioselectivity</subject><subject>gold</subject><subject>Oxidants</subject><subject>Oxidation</subject><subject>Oxidizing agents</subject><subject>Quinoline</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><recordid>eNqFkc9v0zAYhiMEYmNw5YgicRkS7vzbzrEKJatUbSCBOFpu_IV5c50uTmHhr8ejo0JcdrLl73lffdZTFK8JnhGM6ZmNHmYUE46VIupJcUwEJYgpxZ7mO2cMKS3IUfEipevMa43l8-KICipknh4XV00f3OnyHartaMP0C1x57r9fhan84G0aYYAelTa6chFtHH2fIEA7-h9QzsPNFKG8vPPO5kE8q6c29Nuh39r456Hsu5K8l2gRM5deFs86GxK8ejhPiq8fF1_qc7S6bJb1fIVarpRClWwxBkoqLSwHuuaAO2Yp5cJp3oJQHFvpOiUo0w6Is47TjhG25gI7hlt2Upzue_MmtztIo9n41EIINkK_S4YojCtdUaYeRyXjVFZCsYy-_Q-97ndDzB_JFK0441riTM32VDv0KQ3Qme3gN3aYDMHmXpe512UOunLgzUPtbr0Bd8D_-slAtQd--gDTI3VmfrFc_FuO9lmfPd4dsna4MVIxJcy3i8ZITevVp-azadhvccGujQ</recordid><startdate>20141208</startdate><enddate>20141208</enddate><creator>Qian, Deyun</creator><creator>Hu, Haoxiang</creator><creator>Liu, Feng</creator><creator>Tang, Bin</creator><creator>Ye, Weimin</creator><creator>Wang, Yidong</creator><creator>Zhang, Junliang</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><general>Wiley Subscription Services, Inc</general><scope>BSCLL</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>20141208</creationdate><title>Gold(I)-Catalyzed Highly Diastereo- and Enantioselective Alkyne Oxidation/Cyclopropanation of 1,6-Enynes</title><author>Qian, Deyun ; Hu, Haoxiang ; Liu, Feng ; Tang, Bin ; Ye, Weimin ; Wang, Yidong ; Zhang, Junliang</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4777-96c00e21985a4e2b4e0f3a2245d84ce5740a6df75238de1dad42f313b450d30c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>alkyne oxidation</topic><topic>Alkynes</topic><topic>Bearing</topic><topic>carbenoids</topic><topic>Catalysis</topic><topic>Catalysts</topic><topic>Cationic</topic><topic>cyclopropanation</topic><topic>enantioselectivity</topic><topic>gold</topic><topic>Oxidants</topic><topic>Oxidation</topic><topic>Oxidizing agents</topic><topic>Quinoline</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Qian, Deyun</creatorcontrib><creatorcontrib>Hu, Haoxiang</creatorcontrib><creatorcontrib>Liu, Feng</creatorcontrib><creatorcontrib>Tang, Bin</creatorcontrib><creatorcontrib>Ye, Weimin</creatorcontrib><creatorcontrib>Wang, Yidong</creatorcontrib><creatorcontrib>Zhang, Junliang</creatorcontrib><collection>Istex</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>Qian, Deyun</au><au>Hu, Haoxiang</au><au>Liu, Feng</au><au>Tang, Bin</au><au>Ye, Weimin</au><au>Wang, Yidong</au><au>Zhang, Junliang</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Gold(I)-Catalyzed Highly Diastereo- and Enantioselective Alkyne Oxidation/Cyclopropanation of 1,6-Enynes</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew. Chem. Int. Ed</addtitle><date>2014-12-08</date><risdate>2014</risdate><volume>53</volume><issue>50</issue><spage>13751</spage><epage>13755</epage><pages>13751-13755</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><coden>ACIEAY</coden><abstract>A highly enantioselective oxidative cyclopropanation of 1,6‐enynes catalyzed by cationic AuI/chiral phophoramidite complexes is presented. The new method provides convenient access to densely functionalized bicyclo[3.1.0]hexanes bearing three contiguous quaternary and tertiary stereogenic centers with high enantioselectivity (up to e.r. 98:2). Control experiments suggest that the quinoline moiety of the β‐gold vinyloxyquinolinium intermediate in the reaction plays an important role in promoting good enantioselectivity through a transitional auxiliary effect in the transition state.
Playing it safe: A highly enantioselective oxidative cyclopropanation of 1,6‐enynes with cationic AuI/chiral phosphoramidite catalysts provided convenient access to densely functionalized bicyclo[3.1.0]hexanes with three contiguous quaternary and tertiary stereogenic centers (see scheme; up to 92 % yield, e.r. 98:2). Control experiments suggest that the quinoline moiety in the oxidant plays an essential role in the enantioselective cyclopropanation.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>25256143</pmid><doi>10.1002/anie.201407717</doi><tpages>5</tpages><edition>International ed. in English</edition></addata></record> |
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| subjects | alkyne oxidation Alkynes Bearing carbenoids Catalysis Catalysts Cationic cyclopropanation enantioselectivity gold Oxidants Oxidation Oxidizing agents Quinoline |
| title | Gold(I)-Catalyzed Highly Diastereo- and Enantioselective Alkyne Oxidation/Cyclopropanation of 1,6-Enynes |
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