Chiral organosilicon compounds in synthesis. Preparation and stereoselective alkylations of silylcinnamyl carbanions

Abstract

Silylallyl carbanions of type 13 bearing a chiral lithium complexing substituent remote from silicon can be alkylated regio- and stereoselectively at the α-position by small electrophiles in nonpolar solvents. The regiochemical outcome of the reaction was found to be highly dependent on the size of the incoming electrophile. Secondary alkyl halides react preferentially at the γ-center and good levels of stereoselectivity are still obtained in nonpolar solvents despite the rather long distance between the reacting center and the chiral auxiliary. Transformation of the alkylated allylsilanes into optically active alcohols and carboxylic acids may represent a potential synthetic application of the method.