An Efficient CuCN-Catalyzed Synthesis of Optically Active 2,3-Allenols from Optically Active 1-Substituted 4-Chloro-2-butyn-1-ols

Abstract

The sequential treatment of optically active terminal propargylic alcohols with n-BuLi/(HCHO)n and regioselective chlorination afforded the corresponding optically active 4-chloro-2-butyn-1-ols. With R1 being a methyl or an ethyl group, an alternative for the synthesis of the corresponding optically active propargylic alcohols is the Novozym 435-catalyzed kinetic resolution of these racemic 4-chloro-2-butyn-1-ols. The subsequent reaction of these optically active 4-chloro-2-butyn-1-ols with the corresponding Grignard reagents under the catalysis of 5 mol % of CuCN afforded the optically active secondary 2,3-allenols in good yields with up to >99% ee