Synthesis of Trimethylsilyloxy and Hydroxy Compounds From Carbanions and Bis(trimethylsilyl)peroxide

The reactions of bis (trimethylsilyl) peroxide with alkyl, vinyl, alkynyl, aromatic and heteroaromatic anions are described. Depending on the reaction conditions, the trimethylsilyloxy derivatives can be obtained alone or together with the corresponding trimethylsilyl derivatives, which is sometimes the major product. Enolates, generated using magnesium diisopropylamide give the corresponding hydroxycarbonyl compounds in good yields. An attempt to rationalise the above results is given, emphasising the wide use of bis(trimethylsilyl)peroxide in organic synthesis as an electrophilic hydroxylation reagent. © 1988.