Highly Selective Monoalkylation of Active Methylene and Related Derivatives using Alkylsilyl Peroxides by a Catalytic CuI-DMAP System

A new approach for highly selective monoalkylation of active methylene and related derivatives using various types of alkylsilyl peroxides in the presence of copper catalysts under mild conditions has been developed to a synthetically useful level. This approach has a wide substrate scope in terms of both active methylene compounds and alkylsilyl peroxides. In addition, nitroalkanes can also be employed for a copper-catalyzed selective monoalkylation with alkylsilyl peroxides. The participation of radical species was proposed in the present monoalkylation reactions by the mechanistic study.