Thermal and Catalytic Transylidations between Halonium Ylides and Synthesis and Reaction of Stable Aliphatic Chloronium Ylides
Intermolecular transylidation between halonium ylides under thermal and catalytic (rhodium(II) acetate) conditions, which makes it possible to synthesize a hitherto unknown kind of aliphatic chloronium ylides as well as a variety of bromonium and iodonium ylides, was developed. The uncatalyzed therm...
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| Veröffentlicht in: | Journal of the American Chemical Society 2008-02, Vol.130 (7), p.2118-2119 |
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| container_issue | 7 |
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| container_title | Journal of the American Chemical Society |
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| creator | Ochiai, Masahito Tada, Norihiro Okada, Takuya Sota, Atushi Miyamoto, Kazunori |
| description | Intermolecular transylidation between halonium ylides under thermal and catalytic (rhodium(II) acetate) conditions, which makes it possible to synthesize a hitherto unknown kind of aliphatic chloronium ylides as well as a variety of bromonium and iodonium ylides, was developed. The uncatalyzed thermal transylidations of bromonium to iodonium ylides probably involve generation of a reactive carbene :C(SO2CF3)2, being electrophilic in nature. Compared to the bromonium and iodonium ylides, the chloronium ylide serves as a much better progenitor for generation of carbenes (or carbenoids) and efficiently undergoes cyclopropanation of olefins such as cyclooctadiene under uncatalyzed thermal conditions. A greater leaving group ability of the λ3-chloranyl and λ3-bromanyl groups compared to that of the λ3-iodanyl group seems to be responsible for the observed differences in reactivity between these halonium ylides. |
| doi_str_mv | 10.1021/ja074624h |
| format | Article |
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The uncatalyzed thermal transylidations of bromonium to iodonium ylides probably involve generation of a reactive carbene :C(SO2CF3)2, being electrophilic in nature. Compared to the bromonium and iodonium ylides, the chloronium ylide serves as a much better progenitor for generation of carbenes (or carbenoids) and efficiently undergoes cyclopropanation of olefins such as cyclooctadiene under uncatalyzed thermal conditions. 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Am. Chem. Soc</addtitle><description>Intermolecular transylidation between halonium ylides under thermal and catalytic (rhodium(II) acetate) conditions, which makes it possible to synthesize a hitherto unknown kind of aliphatic chloronium ylides as well as a variety of bromonium and iodonium ylides, was developed. The uncatalyzed thermal transylidations of bromonium to iodonium ylides probably involve generation of a reactive carbene :C(SO2CF3)2, being electrophilic in nature. Compared to the bromonium and iodonium ylides, the chloronium ylide serves as a much better progenitor for generation of carbenes (or carbenoids) and efficiently undergoes cyclopropanation of olefins such as cyclooctadiene under uncatalyzed thermal conditions. A greater leaving group ability of the λ3-chloranyl and λ3-bromanyl groups compared to that of the λ3-iodanyl group seems to be responsible for the observed differences in reactivity between these halonium ylides.</description><subject>Alkenes - chemistry</subject><subject>Catalysis</subject><subject>Cyclooctanes - chemical synthesis</subject><subject>Cyclooctanes - chemistry</subject><subject>Cyclopropanes - chemical synthesis</subject><subject>Halogens - chemistry</subject><subject>Hot Temperature</subject><subject>Hydrocarbons - chemical synthesis</subject><subject>Hydrocarbons - chemistry</subject><subject>Hydrocarbons, Halogenated - chemical synthesis</subject><subject>Methane - analogs & derivatives</subject><subject>Methane - chemical synthesis</subject><subject>Methane - chemistry</subject><subject>Rhodium - chemistry</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>eNptkE9v1DAUxC1ERZfCgS-AfAGphxTb8Z_0WKKWIlUFdZcDXKwXr614cZKt7ajdC5-dLFkVDpyeRvObedIg9IaSM0oY_bABorhkvH2GFlQwUgjK5HO0IISwQlWyPEYvU9pMkrOKvkDHtGJUKcEW6NeqtbGDgKFf4xoyhF32Bq8i9GkX_BqyH_qEG5sfrO3xNYSh92OHv0-eTX9Sy12fW5v8rO4smH0GDw4vMzTB4ovgty3sa-s2DPHfglfoyEFI9vXhnqBvV5er-rq4-fLpc31xUwCnKhfcSWKIa1gjSkNoZaVjtJHWlbysuKioMwaEbASpqKgsdYy5KeKcEhQI8PIEvZ97t3G4H23KuvPJ2BCgt8OYtCLsnPLyfAJPZ9DEIaVond5G30HcaUr0fmz9NPbEvj2Ujk1n13_Jw7oTUMyAT9k-PvkQf2qpSiX06utS_7iTt1esvtUfJ_7dzINJejOMsZ82-c_j36Vclqc</recordid><startdate>20080220</startdate><enddate>20080220</enddate><creator>Ochiai, Masahito</creator><creator>Tada, Norihiro</creator><creator>Okada, Takuya</creator><creator>Sota, Atushi</creator><creator>Miyamoto, Kazunori</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></search><sort><creationdate>20080220</creationdate><title>Thermal and Catalytic Transylidations between Halonium Ylides and Synthesis and Reaction of Stable Aliphatic Chloronium Ylides</title><author>Ochiai, Masahito ; Tada, Norihiro ; Okada, Takuya ; Sota, Atushi ; Miyamoto, Kazunori</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a417t-4f60c0fb2b53c018e6f21b6ef34384581fcca56b508158e1f22ff60ff751a0a43</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2008</creationdate><topic>Alkenes - chemistry</topic><topic>Catalysis</topic><topic>Cyclooctanes - chemical synthesis</topic><topic>Cyclooctanes - chemistry</topic><topic>Cyclopropanes - chemical synthesis</topic><topic>Halogens - chemistry</topic><topic>Hot Temperature</topic><topic>Hydrocarbons - chemical synthesis</topic><topic>Hydrocarbons - chemistry</topic><topic>Hydrocarbons, Halogenated - chemical synthesis</topic><topic>Methane - analogs & derivatives</topic><topic>Methane - chemical synthesis</topic><topic>Methane - chemistry</topic><topic>Rhodium - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ochiai, Masahito</creatorcontrib><creatorcontrib>Tada, Norihiro</creatorcontrib><creatorcontrib>Okada, Takuya</creatorcontrib><creatorcontrib>Sota, Atushi</creatorcontrib><creatorcontrib>Miyamoto, Kazunori</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><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ochiai, Masahito</au><au>Tada, Norihiro</au><au>Okada, Takuya</au><au>Sota, Atushi</au><au>Miyamoto, Kazunori</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Thermal and Catalytic Transylidations between Halonium Ylides and Synthesis and Reaction of Stable Aliphatic Chloronium Ylides</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2008-02-20</date><risdate>2008</risdate><volume>130</volume><issue>7</issue><spage>2118</spage><epage>2119</epage><pages>2118-2119</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Intermolecular transylidation between halonium ylides under thermal and catalytic (rhodium(II) acetate) conditions, which makes it possible to synthesize a hitherto unknown kind of aliphatic chloronium ylides as well as a variety of bromonium and iodonium ylides, was developed. The uncatalyzed thermal transylidations of bromonium to iodonium ylides probably involve generation of a reactive carbene :C(SO2CF3)2, being electrophilic in nature. Compared to the bromonium and iodonium ylides, the chloronium ylide serves as a much better progenitor for generation of carbenes (or carbenoids) and efficiently undergoes cyclopropanation of olefins such as cyclooctadiene under uncatalyzed thermal conditions. A greater leaving group ability of the λ3-chloranyl and λ3-bromanyl groups compared to that of the λ3-iodanyl group seems to be responsible for the observed differences in reactivity between these halonium ylides.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>18217752</pmid><doi>10.1021/ja074624h</doi><tpages>2</tpages></addata></record> |
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| source | ACS Publications; MEDLINE |
| subjects | Alkenes - chemistry Catalysis Cyclooctanes - chemical synthesis Cyclooctanes - chemistry Cyclopropanes - chemical synthesis Halogens - chemistry Hot Temperature Hydrocarbons - chemical synthesis Hydrocarbons - chemistry Hydrocarbons, Halogenated - chemical synthesis Methane - analogs & derivatives Methane - chemical synthesis Methane - chemistry Rhodium - chemistry |
| title | Thermal and Catalytic Transylidations between Halonium Ylides and Synthesis and Reaction of Stable Aliphatic Chloronium Ylides |
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