Salt‐Free Preparation of Trimethylsilyl Ethers by B(C₆F₅)₃‐Catalyzed Transfer Silylation by Using a Me₃SiH Surrogate

Abstract

Abstract An unprecedented transfer silylation of alcohols catalyzed by the strong Lewis acid B(C 6 F 5 ) 3 is described. Gaseous Me 3 SiH is released in situ by B(C 6 F 5 ) 3 ‐catalyzed decomposition of 3‐trimethylsilylcyclohexa‐1,4‐diene and subsequently reacts with an alcohol in a dehydrogenative Si–O coupling promoted by the same boron catalyst. Benzene and dihydrogen are formed during the reaction, but no salt waste is. This expedient protocol is applicable to several silicon groups, and the preparation of trimethylsilyl ethers presented here is potentially useful for alcohol derivatization prior to GLC analysis.