Construction of Hexahydrophenanthrenes By Rhodium(I)-Catalyzed Cycloisomerization of Benzylallene-Substituted Internal Alkynes through C−H Activation
The treatment of benzylallene‐substituted internal alkynes with [RhCl(CO)2]2 effects a novel cycloisomerization by C(sp2)−H bond activation to produce hexahydrophenanthrene derivatives. The reaction likely proceeds through consecutive formation of a rhodabicyclo[4.3.0] intermediate, σ‐bond metathesi...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2016-08, Vol.55 (35), p.10473-10477 |
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| creator | Kawaguchi, Yasuaki Yasuda, Shigeo Mukai, Chisato |
| description | The treatment of benzylallene‐substituted internal alkynes with [RhCl(CO)2]2 effects a novel cycloisomerization by C(sp2)−H bond activation to produce hexahydrophenanthrene derivatives. The reaction likely proceeds through consecutive formation of a rhodabicyclo[4.3.0] intermediate, σ‐bond metathesis between the C(sp2)−H bond on the benzene ring and the C(sp2)−RhIII bond, and isomerization between three σ‐, π‐, and σ‐allylrhodium(III) species, which was proposed based on experiments with deuterated substrates.
Hexahydrophenanthrene derivatives were obtained from internal alkynes with a pendant benzylallene moiety through cycloisomerization by C(sp2)−H bond activation. The reaction likely proceeds by formation of a rhodabicyclo[4.3.0] intermediate, σ‐bond metathesis between a C(sp2)−H bond on the benzene ring and the C(sp2)−RhIII bond, and isomerization between three σ‐, π‐, and σ‐allylrhodium(III) species. |
| doi_str_mv | 10.1002/anie.201605640 |
| format | Article |
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Hexahydrophenanthrene derivatives were obtained from internal alkynes with a pendant benzylallene moiety through cycloisomerization by C(sp2)−H bond activation. The reaction likely proceeds by formation of a rhodabicyclo[4.3.0] intermediate, σ‐bond metathesis between a C(sp2)−H bond on the benzene ring and the C(sp2)−RhIII bond, and isomerization between three σ‐, π‐, and σ‐allylrhodium(III) species.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201605640</identifier><identifier>PMID: 27467443</identifier><identifier>CODEN: ACIEAY</identifier><language>eng</language><publisher>Germany: Blackwell Publishing Ltd</publisher><subject>Activation ; Alkynes ; allenes ; Benzene ; Construction ; cycloisomerization ; C−H activation ; Deuteration ; Hydrogen bonds ; Isomerization ; Metathesis ; Rhodium ; Substrates</subject><ispartof>Angewandte Chemie International Edition, 2016-08, Vol.55 (35), p.10473-10477</ispartof><rights>2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5420-ed32c6c91fb2c9f917881bdd07edbdf44eaf5e92edc61f9b01192255ce235d693</citedby><cites>FETCH-LOGICAL-c5420-ed32c6c91fb2c9f917881bdd07edbdf44eaf5e92edc61f9b01192255ce235d693</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.201605640$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201605640$$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/27467443$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kawaguchi, Yasuaki</creatorcontrib><creatorcontrib>Yasuda, Shigeo</creatorcontrib><creatorcontrib>Mukai, Chisato</creatorcontrib><title>Construction of Hexahydrophenanthrenes By Rhodium(I)-Catalyzed Cycloisomerization of Benzylallene-Substituted Internal Alkynes through C−H Activation</title><title>Angewandte Chemie International Edition</title><addtitle>Angew. Chem. Int. Ed</addtitle><description>The treatment of benzylallene‐substituted internal alkynes with [RhCl(CO)2]2 effects a novel cycloisomerization by C(sp2)−H bond activation to produce hexahydrophenanthrene derivatives. The reaction likely proceeds through consecutive formation of a rhodabicyclo[4.3.0] intermediate, σ‐bond metathesis between the C(sp2)−H bond on the benzene ring and the C(sp2)−RhIII bond, and isomerization between three σ‐, π‐, and σ‐allylrhodium(III) species, which was proposed based on experiments with deuterated substrates.
Hexahydrophenanthrene derivatives were obtained from internal alkynes with a pendant benzylallene moiety through cycloisomerization by C(sp2)−H bond activation. The reaction likely proceeds by formation of a rhodabicyclo[4.3.0] intermediate, σ‐bond metathesis between a C(sp2)−H bond on the benzene ring and the C(sp2)−RhIII bond, and isomerization between three σ‐, π‐, and σ‐allylrhodium(III) species.</description><subject>Activation</subject><subject>Alkynes</subject><subject>allenes</subject><subject>Benzene</subject><subject>Construction</subject><subject>cycloisomerization</subject><subject>C−H activation</subject><subject>Deuteration</subject><subject>Hydrogen bonds</subject><subject>Isomerization</subject><subject>Metathesis</subject><subject>Rhodium</subject><subject>Substrates</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNqFkc1u1DAURiMEoqWwZYkisSmLDP6J43g5jUpnpHaQoKhLy4lvSFpPPLUTaOYJWLPh_XgSHKYdIRaw8l2c71xffVH0EqMZRoi8VV0LM4JwhliWokfRIWYEJ5Rz-jjMKaUJzxk-iJ55fx34PEfZ0-iA8DTjaUoPox-F7XzvhqpvbRfbOl7AnWpG7eymgU51feOgAx-fjPGHxup2WB8v3ySF6pUZt6DjYqyMbb1dg2u36kFyAt12NMqYkE0-DqXv237oA77senCdMvHc3IyTN_jt8LmJi5_fvi_iefjGl9-W59GTWhkPL-7fo-jTu9PLYpGcvz9bFvPzpGIpQQloSqqsErguSSVqgXme41JrxEGXuk5TUDUDQUBXGa5FiTAWhDBWAaFMZ4IeRcc778bZ2wF8L9etr8AY1YEdvMQ5JoRwxrKAvv4LvbbDdEygBOIM58H8TyqftqecpIGa7ajKWe8d1HLj2rVyo8RITsXKqVi5LzYEXt1rh3INeo8_NBkAsQO-tgbG_-jkfLU8_VOe7LKt7-Fun1XuRmacciavVmdyRS_IxdXlSgr6C0VDwiw</recordid><startdate>20160822</startdate><enddate>20160822</enddate><creator>Kawaguchi, Yasuaki</creator><creator>Yasuda, Shigeo</creator><creator>Mukai, Chisato</creator><general>Blackwell Publishing Ltd</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></search><sort><creationdate>20160822</creationdate><title>Construction of Hexahydrophenanthrenes By Rhodium(I)-Catalyzed Cycloisomerization of Benzylallene-Substituted Internal Alkynes through C−H Activation</title><author>Kawaguchi, Yasuaki ; Yasuda, Shigeo ; Mukai, Chisato</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5420-ed32c6c91fb2c9f917881bdd07edbdf44eaf5e92edc61f9b01192255ce235d693</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Activation</topic><topic>Alkynes</topic><topic>allenes</topic><topic>Benzene</topic><topic>Construction</topic><topic>cycloisomerization</topic><topic>C−H activation</topic><topic>Deuteration</topic><topic>Hydrogen bonds</topic><topic>Isomerization</topic><topic>Metathesis</topic><topic>Rhodium</topic><topic>Substrates</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kawaguchi, Yasuaki</creatorcontrib><creatorcontrib>Yasuda, Shigeo</creatorcontrib><creatorcontrib>Mukai, Chisato</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><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kawaguchi, Yasuaki</au><au>Yasuda, Shigeo</au><au>Mukai, Chisato</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Construction of Hexahydrophenanthrenes By Rhodium(I)-Catalyzed Cycloisomerization of Benzylallene-Substituted Internal Alkynes through C−H Activation</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew. Chem. Int. Ed</addtitle><date>2016-08-22</date><risdate>2016</risdate><volume>55</volume><issue>35</issue><spage>10473</spage><epage>10477</epage><pages>10473-10477</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><coden>ACIEAY</coden><abstract>The treatment of benzylallene‐substituted internal alkynes with [RhCl(CO)2]2 effects a novel cycloisomerization by C(sp2)−H bond activation to produce hexahydrophenanthrene derivatives. The reaction likely proceeds through consecutive formation of a rhodabicyclo[4.3.0] intermediate, σ‐bond metathesis between the C(sp2)−H bond on the benzene ring and the C(sp2)−RhIII bond, and isomerization between three σ‐, π‐, and σ‐allylrhodium(III) species, which was proposed based on experiments with deuterated substrates.
Hexahydrophenanthrene derivatives were obtained from internal alkynes with a pendant benzylallene moiety through cycloisomerization by C(sp2)−H bond activation. The reaction likely proceeds by formation of a rhodabicyclo[4.3.0] intermediate, σ‐bond metathesis between a C(sp2)−H bond on the benzene ring and the C(sp2)−RhIII bond, and isomerization between three σ‐, π‐, and σ‐allylrhodium(III) species.</abstract><cop>Germany</cop><pub>Blackwell Publishing Ltd</pub><pmid>27467443</pmid><doi>10.1002/anie.201605640</doi><tpages>5</tpages><edition>International ed. in English</edition></addata></record> |
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| source | Wiley Online Library - AutoHoldings Journals |
| subjects | Activation Alkynes allenes Benzene Construction cycloisomerization C−H activation Deuteration Hydrogen bonds Isomerization Metathesis Rhodium Substrates |
| title | Construction of Hexahydrophenanthrenes By Rhodium(I)-Catalyzed Cycloisomerization of Benzylallene-Substituted Internal Alkynes through C−H Activation |
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