Making the Silylation of Alcohols Chiral: Asymmetric Protection of Hydroxy Groups

The non-enzymatic kinetic resolution of racemic mixtures of alcohols by silylation had been unknown before the turn of the century. This stands in stark contrast to established acylation techniques. The same applies to the related desymmetrization of diols. This might come as a surprise, given the significance of silyl ethers as protecting groups in multistep synthesis of complex molecules. The situation changed after a seminal report by Ishikawa nearly twenty years ago. Since then, enantioselective silylation of alcohols has matured and grown into an independent research field with organocatalytic and transition-metal-catalyzed approaches providing powerful solutions. This Minireview summarizes these recent advances with particular emphasis on the stereoselective dehydrogenative coupling of alcohols and hydrosilanes.