Atroposelective Silylation of 1,1′-Biaryl-2,6-diols by a Chiral Counteranion Directed Desymmetrization Enhanced by a Subsequent Kinetic Resolution

Abstract

A desymmetrizing silylation of aromatic diols is reported. The previously unknown asymmetric silyl ether formation of phenol derivatives is achieved by applying List's counteranion directed silylation technique. A silylium-ion-like silicon electrophile generated from an allylic silane paired with an imidodiphosphorimidate (IDPi) enables enantioselective discrimination of achiral 1,1′-biaryl-2,6-diols. The enantioselectivity of that desymmetrization is further improved by a downstream kinetic resolution, converting the monosilylated minor enantiomer into the corresponding, again achiral bissilylated diol.