A nonenzymatic kinetic resolution of sterically congested alcohols having a quaternary carbon atom in the β-position is reported. The catalyst system CuCl/NaOtBu/(R,R)-Ph-BPE together with a 3,5-xylyl-substituted tertiary hydrosilane enable enantioselective silylation of the hydroxy group. Several alcohols are obtained with good to excellent selectivity factors, and there are no other known straightforward methods to access these motifs.

Procedures for the utilization of ferri-/ferrocyanide, α-amino acids, aliphatic nitriles and cyanohydrins as universal and often non-toxic cyanide sources have been developed.

An enantio-and diastereoselective Cu−H-catalyzed silylation of acyclic secondary alcohols with a vicinal quaternary stereocenter is reported. The reaction kinetically selects one out of four stereoisomers, affording the fastest-reacting stereoisomer as the silyl ether in enantio-and diastereomerically enriched form. The obtained motif with a quaternary carbon atom in the βposition of the hydroxy group is otherwise not easy to access.