The Lewis Base-Catalyzed Silylation of Alcohols-A Mechanistic Analysis
The Lewis Base-Catalyzed Silylation of Alcohols-A Mechanistic Analysis
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DOI：
10.1021/jo5016568
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发表时间：
2014-09-05
影响因子：
3.6
通讯作者：
Zipse, Hendrik
中科院分区：
文献类型：
--
作者：
Patschinski, Pascal;Zhang, Cong;Zipse, Hendrik
伯醇、仲醇和叔醇的碱催化硅烷化反应速率强烈依赖于溶剂和催化剂的选择。在Lewis碱性溶剂如二甲基甲酰胺(DMF)中的反应比在氯仿或二氯甲烷(DCM)中的反应快得多。在DMF溶剂中，伯醇、仲醇和叔醇的反应半衰期之比为404345：20232：1。添加Lewis碱催化剂，如4-N，N-二甲氨基吡啶或4-吡咯烷基吡啶，在非极性溶剂中的影响比在DMF中大得多。需要三乙胺等辅助碱的存在才能使反应完全转化。
Reaction rates for the base-catalyzed silylation of primary, secondary, and tertiary alcohols depend strongly on the choice of solvent and catalyst. The reactions are significantly faster in Lewis basic solvents such as dimethylformamide (DMF) compared with those in chloroform or dichloromethane (DCM). In DMF as the solvent, the reaction half-lives for the conversion of structurally similar primary, secondary, and tertiary alcohols vary in the ratio 404345:20232:1. The effects of added Lewis base catalysts such as 4-N,N-dimethylaminopyridine (DMAP) or 4-pyrrolidinopyridine (PPY) are much larger in apolar solvents than in DMF. The presence of an auxiliary base such as triethylamine is required in order to drive the reaction to full conversion.