ORGN 175 |
| Allyl- and vinylsilanes are among the most important intermediates in organic chemistry. Recently, we have reported the regio- and chemoselective silyl-zincation of terminal alkenes and alkynes using newly developed dianion-type zincates. In this presentation, we would like to report the silyl-zincation of 1-substituted allenes, which have the potential for the synthesis of allyl- and vinylsilanes. Our initial studies using 1-phenylallene (1) as a model substrate, aimed at identifying favorable reaction conditions, revealed that a dimethylphenylsilyl (DMPS) group as the silyl moiety and THF as a solvent were suitable starting points for optimization of the silyl-zincation reaction conditions. After extensive experimentation, we found two effective reagents, DMPS-Zn-Me and (DMPS)3ZnLi that reacted 1 smoothly at room temperature without any transition metal catalysts to give branched and linear vinylsilanes, respectively. |
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Asymmetric Reactions and Syntheses, Metal-Mediated Reactions, Combinatorial, Parallel, and Solid-Phase Chemistry
8:00 PM-10:00 PM, Sunday, 10 September 2006 Moscone Center -- Hall D, Poster
Division of Organic Chemistry |