Rhodium(I)-Catalyzed Cyclization of Allenynes with a Carbonyl Group through Unusual Insertion of a CO Bond into a Rhodacycle Intermediate

Rhodium(I)‐catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a CO bond into the C(sp2)–rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermed...

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Veröffentlicht in:	Angewandte Chemie International Edition 2014-01, Vol.53 (4), p.1135-1139
Hauptverfasser:	Oonishi, Yoshihiro, Yokoe, Takayuki, Hosotani, Akihito, Sato, Yoshihiro
Format:	Artikel
Sprache:	eng
Schlagworte:	alkynes Alkynes - chemistry allenes Bonding Bridged Bicyclo Compounds, Heterocyclic - chemical synthesis Bridged Bicyclo Compounds, Heterocyclic - chemistry carbonyl compounds Carbonyl groups Catalysis Cyclization cycloadditions Direct reduction Insertion Molecular Structure Organometallic Compounds - chemistry rhodium Rhodium - chemistry
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creator	Oonishi, Yoshihiro Yokoe, Takayuki Hosotani, Akihito Sato, Yoshihiro
description	Rhodium(I)‐catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a CO bond into the C(sp2)–rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8‐oxabicyclo[3.2.1]octane skeleton, while β‐hydride elimination from the same intermediate gives products that contain fused five‐ and seven‐membered rings in high yields. Unusual insertion: During the title reaction, a CO bond is inserted into the C(sp2)Rh bond of rhodacycle intermediate I. The insertion occurs via a highly strained transition state. Direct reductive elimination from II gives a tricyclic product containing an 8‐oxabicyclo[3.2.1]octane skeleton, whereas β‐hydride elimination from II gives products with fused five‐ and seven‐membered rings.
doi_str_mv	10.1002/anie.201308824
format	Article
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An unusual insertion of a CO bond into the C(sp2)–rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8‐oxabicyclo[3.2.1]octane skeleton, while β‐hydride elimination from the same intermediate gives products that contain fused five‐ and seven‐membered rings in high yields. Unusual insertion: During the title reaction, a CO bond is inserted into the C(sp2)Rh bond of rhodacycle intermediate I. The insertion occurs via a highly strained transition state. Direct reductive elimination from II gives a tricyclic product containing an 8‐oxabicyclo[3.2.1]octane skeleton, whereas β‐hydride elimination from II gives products with fused five‐ and seven‐membered rings.</description><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201308824</identifier><identifier>PMID: 24307141</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>alkynes ; Alkynes - chemistry ; allenes ; Bonding ; Bridged Bicyclo Compounds, Heterocyclic - chemical synthesis ; Bridged Bicyclo Compounds, Heterocyclic - chemistry ; carbonyl compounds ; Carbonyl groups ; Catalysis ; Cyclization ; cycloadditions ; Direct reduction ; Insertion ; Molecular Structure ; Organometallic Compounds - chemistry ; rhodium ; Rhodium - chemistry</subject><ispartof>Angewandte Chemie International Edition, 2014-01, Vol.53 (4), p.1135-1139</ispartof><rights>Copyright © 2014 WILEY‐VCH Verlag GmbH & Co. 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Chem. Int. Ed</addtitle><description>Rhodium(I)‐catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a CO bond into the C(sp2)–rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8‐oxabicyclo[3.2.1]octane skeleton, while β‐hydride elimination from the same intermediate gives products that contain fused five‐ and seven‐membered rings in high yields. Unusual insertion: During the title reaction, a CO bond is inserted into the C(sp2)Rh bond of rhodacycle intermediate I. The insertion occurs via a highly strained transition state. Direct reductive elimination from II gives a tricyclic product containing an 8‐oxabicyclo[3.2.1]octane skeleton, whereas β‐hydride elimination from II gives products with fused five‐ and seven‐membered rings.</description><subject>alkynes</subject><subject>Alkynes - chemistry</subject><subject>allenes</subject><subject>Bonding</subject><subject>Bridged Bicyclo Compounds, Heterocyclic - chemical synthesis</subject><subject>Bridged Bicyclo Compounds, Heterocyclic - chemistry</subject><subject>carbonyl compounds</subject><subject>Carbonyl groups</subject><subject>Catalysis</subject><subject>Cyclization</subject><subject>cycloadditions</subject><subject>Direct reduction</subject><subject>Insertion</subject><subject>Molecular Structure</subject><subject>Organometallic Compounds - chemistry</subject><subject>rhodium</subject><subject>Rhodium - chemistry</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>eNqFkc9u1DAQxi0Eou3ClSPysRyy-E-cOMclKstKpZUqKqReLMexWYPXXuxEJX2GvgXvwSvxCni17Ypb5zKj0e_7RpoPgDcYzTFC5L30Vs8JwhRxTspn4Bgzggta1_R5nktKi5ozfAROUvqeec5R9RIckZKiGpf4GNxfrUNvx83p6l3RykG66U73sJ2Us3dysMHDYODCOe0nrxO8tcMaStjK2AU_ObiMYdzCYZ3btzW89mMapYMrn3R8FGf67-8_l_BD8D20fgh5szsqVT6iMzvouNG9lYN-BV4Y6ZJ-_dBn4Prj2Zf2U3F-uVy1i_NClYyWBeN9pbhBNcGkZz1udNcYbLRB2lBODGsq1GlmGKdcKdTnkaualMaojlKM6Ayc7n23MfwcdRrExialnZNehzEJXCOMMWMVfxotG4xYQ3PNwHyPqhhSitqIbbQbGSeBkdiFJXZhiUNYWfD2wXvs8gcO-GM6GWj2wK11enrCTiwuVmf_mxd7rU2D_nXQyvhDVDWtmfh6sRSfGcVX5OZGcPoPCUqyCw</recordid><startdate>20140120</startdate><enddate>20140120</enddate><creator>Oonishi, Yoshihiro</creator><creator>Yokoe, Takayuki</creator><creator>Hosotani, Akihito</creator><creator>Sato, Yoshihiro</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</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>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope></search><sort><creationdate>20140120</creationdate><title>Rhodium(I)-Catalyzed Cyclization of Allenynes with a Carbonyl Group through Unusual Insertion of a CO Bond into a Rhodacycle Intermediate</title><author>Oonishi, Yoshihiro ; Yokoe, Takayuki ; Hosotani, Akihito ; Sato, Yoshihiro</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4534-58d6c8f07212d5d19eb9f1fef0ef382f5960be5f5838cc0de5f8c724ffcb33103</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>alkynes</topic><topic>Alkynes - chemistry</topic><topic>allenes</topic><topic>Bonding</topic><topic>Bridged Bicyclo Compounds, Heterocyclic - chemical synthesis</topic><topic>Bridged Bicyclo Compounds, Heterocyclic - chemistry</topic><topic>carbonyl compounds</topic><topic>Carbonyl groups</topic><topic>Catalysis</topic><topic>Cyclization</topic><topic>cycloadditions</topic><topic>Direct reduction</topic><topic>Insertion</topic><topic>Molecular Structure</topic><topic>Organometallic Compounds - chemistry</topic><topic>rhodium</topic><topic>Rhodium - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Oonishi, Yoshihiro</creatorcontrib><creatorcontrib>Yokoe, Takayuki</creatorcontrib><creatorcontrib>Hosotani, Akihito</creatorcontrib><creatorcontrib>Sato, Yoshihiro</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>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>Oonishi, Yoshihiro</au><au>Yokoe, Takayuki</au><au>Hosotani, Akihito</au><au>Sato, Yoshihiro</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Rhodium(I)-Catalyzed Cyclization of Allenynes with a Carbonyl Group through Unusual Insertion of a CO Bond into a Rhodacycle Intermediate</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew. Chem. Int. Ed</addtitle><date>2014-01-20</date><risdate>2014</risdate><volume>53</volume><issue>4</issue><spage>1135</spage><epage>1139</epage><pages>1135-1139</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>Rhodium(I)‐catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a CO bond into the C(sp2)–rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8‐oxabicyclo[3.2.1]octane skeleton, while β‐hydride elimination from the same intermediate gives products that contain fused five‐ and seven‐membered rings in high yields. Unusual insertion: During the title reaction, a CO bond is inserted into the C(sp2)Rh bond of rhodacycle intermediate I. The insertion occurs via a highly strained transition state. Direct reductive elimination from II gives a tricyclic product containing an 8‐oxabicyclo[3.2.1]octane skeleton, whereas β‐hydride elimination from II gives products with fused five‐ and seven‐membered rings.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>24307141</pmid><doi>10.1002/anie.201308824</doi><tpages>5</tpages></addata></record>
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subjects	alkynes Alkynes - chemistry allenes Bonding Bridged Bicyclo Compounds, Heterocyclic - chemical synthesis Bridged Bicyclo Compounds, Heterocyclic - chemistry carbonyl compounds Carbonyl groups Catalysis Cyclization cycloadditions Direct reduction Insertion Molecular Structure Organometallic Compounds - chemistry rhodium Rhodium - chemistry
title	Rhodium(I)-Catalyzed Cyclization of Allenynes with a Carbonyl Group through Unusual Insertion of a CO Bond into a Rhodacycle Intermediate
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