Asymmetric Synthesis of Bicyclic Amidines via Rhodium-Catalyzed [2+2+2] Cycloaddition of Carbodiimides
A highly enantioselective rhodium-catalyzed [2+2+2] cycloaddition of terminal alkynes and alkenyl carbodiimides has been developed. This reaction demonstrates the feasibility of olefin insertion into carbodiimide-derived metalacycles and provides a new class of chiral bicyclic amidines as the major...
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| Veröffentlicht in: | Journal of the American Chemical Society 2008-03, Vol.130 (11), p.3262-3263 |
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| container_end_page | 3263 |
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| container_issue | 11 |
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| container_title | Journal of the American Chemical Society |
| container_volume | 130 |
| creator | Yu, Robert T Rovis, Tomislav |
| description | A highly enantioselective rhodium-catalyzed [2+2+2] cycloaddition of terminal alkynes and alkenyl carbodiimides has been developed. This reaction demonstrates the feasibility of olefin insertion into carbodiimide-derived metalacycles and provides a new class of chiral bicyclic amidines as the major products. An isonitrile migration process responsible for the formation of the minor cycloadduct can be observed and is highly sensitive to the electronics of alkynyl substrates. |
| doi_str_mv | 10.1021/ja710065h |
| format | Article |
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This reaction demonstrates the feasibility of olefin insertion into carbodiimide-derived metalacycles and provides a new class of chiral bicyclic amidines as the major products. An isonitrile migration process responsible for the formation of the minor cycloadduct can be observed and is highly sensitive to the electronics of alkynyl substrates.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja710065h</identifier><identifier>PMID: 18302377</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Alkynes - chemistry ; Amidines - chemical synthesis ; Amidines - chemistry ; Bridged Bicyclo Compounds - chemical synthesis ; Bridged Bicyclo Compounds - chemistry ; Carbodiimides - chemistry ; Catalysis ; Cyclization ; Ligands ; Molecular Structure ; Rhodium - chemistry ; Stereoisomerism</subject><ispartof>Journal of the American Chemical Society, 2008-03, Vol.130 (11), p.3262-3263</ispartof><rights>Copyright © 2008 American Chemical Society</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a507t-865aa710a1e7ebf70fd16f2770fd4fd856c1fbd210821e96d9cd631b764385293</citedby><cites>FETCH-LOGICAL-a507t-865aa710a1e7ebf70fd16f2770fd4fd856c1fbd210821e96d9cd631b764385293</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/ja710065h$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja710065h$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,780,784,885,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/18302377$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Yu, Robert T</creatorcontrib><creatorcontrib>Rovis, Tomislav</creatorcontrib><title>Asymmetric Synthesis of Bicyclic Amidines via Rhodium-Catalyzed [2+2+2] Cycloaddition of Carbodiimides</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>A highly enantioselective rhodium-catalyzed [2+2+2] cycloaddition of terminal alkynes and alkenyl carbodiimides has been developed. This reaction demonstrates the feasibility of olefin insertion into carbodiimide-derived metalacycles and provides a new class of chiral bicyclic amidines as the major products. An isonitrile migration process responsible for the formation of the minor cycloadduct can be observed and is highly sensitive to the electronics of alkynyl substrates.</description><subject>Alkynes - chemistry</subject><subject>Amidines - chemical synthesis</subject><subject>Amidines - chemistry</subject><subject>Bridged Bicyclo Compounds - chemical synthesis</subject><subject>Bridged Bicyclo Compounds - chemistry</subject><subject>Carbodiimides - chemistry</subject><subject>Catalysis</subject><subject>Cyclization</subject><subject>Ligands</subject><subject>Molecular Structure</subject><subject>Rhodium - chemistry</subject><subject>Stereoisomerism</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2008</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkV1L5DAUhoO46Phx4R-Q3ijIUk3SadLeCGNxZhcExVG8EAlpPpyMbTMmrWz312-GGWYVJBf5OM95z8l5AThC8BxBjC7mnCIISTrbAgOUYhinCJNtMIAQ4phmJNkFe97Pw3WIM7QDdlGWQJxQOgB65Pu6Vq0zIpr2TTtT3vjI6ujKiF5U4XVUG2ka5aMPw6P7mZWmq-OCt7zq_yoZPeOfYb1ERaAtl9K0xjZLgYK7MsAmpCt_AH5oXnl1uN73weP4-qH4Fd_cTn4Xo5uYp5C2cUZSvvwLR4qqUlOoJSIa0-VhqGWWEoF0KTGCGUYqJzIXkiSopGSYZCnOk31wudJddGWtpFBN63jFFs7U3PXMcsO-RhozY6_2g-Ec0TCVIHC6FnD2vVO-ZbXxQlUVb5TtPKMwyXHoI4BnK1A4671TelMEQbZ0hW1cCezx567-k2sbAhCvAONb9WcT5-6NEZrQlD3cTdlk_HQ3HD9lbBz4kxXPhWdz27kmDPWbwv8AcXmj3w</recordid><startdate>20080319</startdate><enddate>20080319</enddate><creator>Yu, Robert T</creator><creator>Rovis, Tomislav</creator><general>American Chemical Society</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><scope>5PM</scope></search><sort><creationdate>20080319</creationdate><title>Asymmetric Synthesis of Bicyclic Amidines via Rhodium-Catalyzed [2+2+2] Cycloaddition of Carbodiimides</title><author>Yu, Robert T ; Rovis, Tomislav</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a507t-865aa710a1e7ebf70fd16f2770fd4fd856c1fbd210821e96d9cd631b764385293</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2008</creationdate><topic>Alkynes - chemistry</topic><topic>Amidines - chemical synthesis</topic><topic>Amidines - chemistry</topic><topic>Bridged Bicyclo Compounds - chemical synthesis</topic><topic>Bridged Bicyclo Compounds - chemistry</topic><topic>Carbodiimides - chemistry</topic><topic>Catalysis</topic><topic>Cyclization</topic><topic>Ligands</topic><topic>Molecular Structure</topic><topic>Rhodium - chemistry</topic><topic>Stereoisomerism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Yu, Robert T</creatorcontrib><creatorcontrib>Rovis, Tomislav</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><collection>PubMed Central (Full Participant titles)</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Yu, Robert T</au><au>Rovis, Tomislav</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Asymmetric Synthesis of Bicyclic Amidines via Rhodium-Catalyzed [2+2+2] Cycloaddition of Carbodiimides</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2008-03-19</date><risdate>2008</risdate><volume>130</volume><issue>11</issue><spage>3262</spage><epage>3263</epage><pages>3262-3263</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>A highly enantioselective rhodium-catalyzed [2+2+2] cycloaddition of terminal alkynes and alkenyl carbodiimides has been developed. This reaction demonstrates the feasibility of olefin insertion into carbodiimide-derived metalacycles and provides a new class of chiral bicyclic amidines as the major products. An isonitrile migration process responsible for the formation of the minor cycloadduct can be observed and is highly sensitive to the electronics of alkynyl substrates.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>18302377</pmid><doi>10.1021/ja710065h</doi><tpages>2</tpages><oa>free_for_read</oa></addata></record> |
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| identifier | ISSN: 0002-7863 |
| ispartof | Journal of the American Chemical Society, 2008-03, Vol.130 (11), p.3262-3263 |
| issn | 0002-7863 1520-5126 |
| language | eng |
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| source | MEDLINE; American Chemical Society Journals |
| subjects | Alkynes - chemistry Amidines - chemical synthesis Amidines - chemistry Bridged Bicyclo Compounds - chemical synthesis Bridged Bicyclo Compounds - chemistry Carbodiimides - chemistry Catalysis Cyclization Ligands Molecular Structure Rhodium - chemistry Stereoisomerism |
| title | Asymmetric Synthesis of Bicyclic Amidines via Rhodium-Catalyzed [2+2+2] Cycloaddition of Carbodiimides |
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