Silicon-Stereogenic Silanes in Asymmetric Catalysis

The exploitation of chirality at silicon in asymmetric ­catalysis is a challenging task. Silicon-stereogenic silanes were initially utilized to elucidate the stereochemical course of substitution at silicon. These mechanistic investigations are to be seen alongside a handful of synthetic transformations with covalently bound ­silicon as the stereoinducer. While in these substrate-controlled reactions the asymmetrically substituted silicon functions as a chiral auxiliary, reagent-controlled processes have remained elusive. This account summarizes the aimed design of silicon-stereogenic silanes and their introduction to stereoselective synthesis as chiral reagents.