Scope and mechanism of stannylalumination of 1-alkynes
Terminal acetylenes react with Bu{sub 3}SnAlEt{sub 2} in the presence of Cu{sup +} or Pd{sup 0} catalysts to give 1,2-dimetallo-1-alkenes in highly regio- and stereoselective reactions. These intermediates can be selectively functionalized at the vinyl-aluminum bond to provide vinylstannanes, which...
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| Veröffentlicht in: | Journal of organic chemistry 1989-10, Vol.54 (21), p.5064-5073 |
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| container_end_page | 5073 |
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| container_issue | 21 |
| container_start_page | 5064 |
| container_title | Journal of organic chemistry |
| container_volume | 54 |
| creator | Sharma, Sunaina Oehlschlager, Allan C |
| description | Terminal acetylenes react with Bu{sub 3}SnAlEt{sub 2} in the presence of Cu{sup +} or Pd{sup 0} catalysts to give 1,2-dimetallo-1-alkenes in highly regio- and stereoselective reactions. These intermediates can be selectively functionalized at the vinyl-aluminum bond to provide vinylstannanes, which upon transmetalation and further reaction with electrophiles give stereodefined trisubstituted olefins. In sharp contrast to the normal behavior of alkylaluminum reagents, this process tolerates a number of functional groups including OH, OAc, OTHP, and Br. Mechanistic investigations suggest that the addition of Bu{sub 3}SnAlEt{sub 2} to 1-alkynes proceeds via stannylcupration followed by capture of the stannylcuprate adduct by electrophilic aluminum. |
| doi_str_mv | 10.1021/jo00282a021 |
| format | Article |
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These intermediates can be selectively functionalized at the vinyl-aluminum bond to provide vinylstannanes, which upon transmetalation and further reaction with electrophiles give stereodefined trisubstituted olefins. In sharp contrast to the normal behavior of alkylaluminum reagents, this process tolerates a number of functional groups including OH, OAc, OTHP, and Br. 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Org. Chem</addtitle><description>Terminal acetylenes react with Bu{sub 3}SnAlEt{sub 2} in the presence of Cu{sup +} or Pd{sup 0} catalysts to give 1,2-dimetallo-1-alkenes in highly regio- and stereoselective reactions. These intermediates can be selectively functionalized at the vinyl-aluminum bond to provide vinylstannanes, which upon transmetalation and further reaction with electrophiles give stereodefined trisubstituted olefins. In sharp contrast to the normal behavior of alkylaluminum reagents, this process tolerates a number of functional groups including OH, OAc, OTHP, and Br. 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Org. Chem</addtitle><date>1989-10-01</date><risdate>1989</risdate><volume>54</volume><issue>21</issue><spage>5064</spage><epage>5073</epage><pages>5064-5073</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><abstract>Terminal acetylenes react with Bu{sub 3}SnAlEt{sub 2} in the presence of Cu{sup +} or Pd{sup 0} catalysts to give 1,2-dimetallo-1-alkenes in highly regio- and stereoselective reactions. These intermediates can be selectively functionalized at the vinyl-aluminum bond to provide vinylstannanes, which upon transmetalation and further reaction with electrophiles give stereodefined trisubstituted olefins. In sharp contrast to the normal behavior of alkylaluminum reagents, this process tolerates a number of functional groups including OH, OAc, OTHP, and Br. Mechanistic investigations suggest that the addition of Bu{sub 3}SnAlEt{sub 2} to 1-alkynes proceeds via stannylcupration followed by capture of the stannylcuprate adduct by electrophilic aluminum.</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/jo00282a021</doi><tpages>10</tpages></addata></record> |
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| identifier | ISSN: 0022-3263 |
| ispartof | Journal of organic chemistry, 1989-10, Vol.54 (21), p.5064-5073 |
| issn | 0022-3263 1520-6904 |
| language | eng |
| recordid | cdi_osti_scitechconnect_7071609 |
| source | ACS Publications |
| subjects | 400201 - Chemical & Physicochemical Properties ACETYLENE ALKYNES ALUMINIUM COMPOUNDS CATALYSTS COPPER DATA DATA ANALYSIS ELEMENTS EXPERIMENTAL DATA HYDROCARBONS INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY MEASURING INSTRUMENTS MEASURING METHODS METALS NUMERICAL DATA ORGANIC COMPOUNDS ORGANOMETALLIC COMPOUNDS PALLADIUM PLATINUM METALS SYNTHESIS TIN COMPOUNDS TRANSITION ELEMENTS |
| title | Scope and mechanism of stannylalumination of 1-alkynes |
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