摘要/Abstract

以四丁基溴化铵作为相转移催化剂，开发了α-硅醇化合物的一种新型布鲁克重排/烷基化反应.多种结构类型的α-硅醇化合物都适用于该反应，高产率（产率高达71%）地合成了具有季碳中心的反应产物.此外，通过酯基官能团的吸电子作用可以稳定布鲁克重排之后生成的碳负离子，而竞争性的布鲁克重排/质子化反应被抑制.
关键词: 相转移催化, 双分子亲核取代反应(S_N2), 烷基化反应, 布鲁克重排反应
A novel Brook rearrangement/alkylation reaction sequence of tertiary α-silyl alcohols has been developed using n-Bu₄NBr as the phase transfer catalyst (PTC). A number of tertiary α-silyl alcohols are applicable to the reaction, affording the products with a quaternary carbon center in high yields (up to 71%). Moreover, the carbanions generated after the Brook rearrangement could be stabilized by the electron-withdrawing group, depressing the Brook rearrangement/protonation reaction.
Key words: phase transfer catalysis, bimolecular nucleophilic substitution (S_N2) reaction, alkylation, Brook rearrangement


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