Catalytic Asymmetric Syntheses of Quinolizidines by Dirhodium-Catalyzed Dearomatization of Isoquinolinium/Pyridinium Methylides–The Role of Catalyst and Carbene Source
Convenient access to highly enantioenriched substituted quinolizidines has been achieved by chiral dirhodium(II) carboxylate-catalyzed dearomatizing formal [3 + 3]-cycloaddition of isoquinolinium/pyridinium methylides and enol diazoacetates. Coordination of Lewis basic methylides to dirhodium(II) pr...
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| Veröffentlicht in: | Journal of the American Chemical Society 2013-08, Vol.135 (33), p.12439-12447 |
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| container_title | Journal of the American Chemical Society |
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| creator | Xu, Xichen Zavalij, Peter Y Doyle, Michael P |
| description | Convenient access to highly enantioenriched substituted quinolizidines has been achieved by chiral dirhodium(II) carboxylate-catalyzed dearomatizing formal [3 + 3]-cycloaddition of isoquinolinium/pyridinium methylides and enol diazoacetates. Coordination of Lewis basic methylides to dirhodium(II) prompts the rearrangement of the enol-carbene that is bound to dirhodium to produce a donor–acceptor cyclopropene. The donor–acceptor cyclopropene is in equilibrium with the dirhodium-bound enol-carbene and undergoes both enantioselective [3 + 3]-cycloaddition from the dirhodium-bound enol-carbene and diastereoselective [3 + 2]-cycloaddition by uncatalyzed reaction of the cyclopropene with isoquinolinium or pyridinium methylides. Increasing the mol % of catalyst loading suppresses the [3 + 2]-cycloaddition pathway. |
| doi_str_mv | 10.1021/ja406482q |
| format | Article |
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Coordination of Lewis basic methylides to dirhodium(II) prompts the rearrangement of the enol-carbene that is bound to dirhodium to produce a donor–acceptor cyclopropene. The donor–acceptor cyclopropene is in equilibrium with the dirhodium-bound enol-carbene and undergoes both enantioselective [3 + 3]-cycloaddition from the dirhodium-bound enol-carbene and diastereoselective [3 + 2]-cycloaddition by uncatalyzed reaction of the cyclopropene with isoquinolinium or pyridinium methylides. 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Increasing the mol % of catalyst loading suppresses the [3 + 2]-cycloaddition pathway.</description><subject>Catalysis</subject><subject>Methane - analogs & derivatives</subject><subject>Methane - chemistry</subject><subject>Models, Molecular</subject><subject>Molecular Conformation</subject><subject>Pyridines - chemistry</subject><subject>Quinolizidines - chemistry</subject><subject>Rhodium - chemistry</subject><subject>Stereoisomerism</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkU1O5DAQhS3ECHqABRcYeTMSs8hgO07iLFHzM0iMhp_eR-64rHYrscF2FukVd-AUXIuT4FYYVixKVWV978mlh9AxJb8pYfR0LTkpuWBPO2hGC0aygrJyF80IISyrRJnvo-8hrNPKmaB7aJ_lQtSE0xl6ncsouzGaFp-Fse8h-jQ-jDauIEDATuO7wVjXmY1RxqaX5YjPjV85ZYY-m9QbUPgcpHe9jGaTytmt8Dq4p0lrE3t6O_qtRRrxX4irsTMKwtvzy2IF-N51sJVMfiFiaVVa_BIs4Ac3-BYO0TctuwBHH_0ALS4vFvM_2c2_q-v52U0mc0Fjxguh80KXUC9LWlCl6pwXVAPjlay54nnFdK1VKQrgoKpWSk0oiLattRalzA_QyWT76NPvIcSmN6GFrpMW3BAayllFSFVWJKG_JrT1LgQPunn0ppd-bChptsE0n8Ek9seH7bDsQX2S_5NIwM8JkG1o1ulim478wugdO8iacg</recordid><startdate>20130821</startdate><enddate>20130821</enddate><creator>Xu, Xichen</creator><creator>Zavalij, Peter Y</creator><creator>Doyle, Michael P</creator><general>American Chemical Society</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></search><sort><creationdate>20130821</creationdate><title>Catalytic Asymmetric Syntheses of Quinolizidines by Dirhodium-Catalyzed Dearomatization of Isoquinolinium/Pyridinium Methylides–The Role of Catalyst and Carbene Source</title><author>Xu, Xichen ; Zavalij, Peter Y ; Doyle, Michael P</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a381t-458f35f6e9b6151dd93451fe247a94d4372f9fd685e4ed7caaf01e8cc9ff86a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2013</creationdate><topic>Catalysis</topic><topic>Methane - analogs & derivatives</topic><topic>Methane - chemistry</topic><topic>Models, Molecular</topic><topic>Molecular Conformation</topic><topic>Pyridines - chemistry</topic><topic>Quinolizidines - chemistry</topic><topic>Rhodium - chemistry</topic><topic>Stereoisomerism</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Xu, Xichen</creatorcontrib><creatorcontrib>Zavalij, Peter Y</creatorcontrib><creatorcontrib>Doyle, Michael P</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><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Xu, Xichen</au><au>Zavalij, Peter Y</au><au>Doyle, Michael P</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Catalytic Asymmetric Syntheses of Quinolizidines by Dirhodium-Catalyzed Dearomatization of Isoquinolinium/Pyridinium Methylides–The Role of Catalyst and Carbene Source</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. 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Increasing the mol % of catalyst loading suppresses the [3 + 2]-cycloaddition pathway.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>23889041</pmid><doi>10.1021/ja406482q</doi><tpages>9</tpages></addata></record> |
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| source | MEDLINE; ACS Publications |
| subjects | Catalysis Methane - analogs & derivatives Methane - chemistry Models, Molecular Molecular Conformation Pyridines - chemistry Quinolizidines - chemistry Rhodium - chemistry Stereoisomerism |
| title | Catalytic Asymmetric Syntheses of Quinolizidines by Dirhodium-Catalyzed Dearomatization of Isoquinolinium/Pyridinium Methylides–The Role of Catalyst and Carbene Source |
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