Kinetic Resolution of BINOLs and Biphenols by Atroposelective, Cu–H-Catalyzed Si–O Coupling with Hydrosilanes

A nonenzymatic kinetic resolution of monoprotected BINOL and biphenol derivatives by atroposelective Si-O coupling with hydrosilanes is described. The reaction relies on a previously unprecedented Cu-H-catalyzed silylation of phenols. The catalyst system consisting of CuCl, (<i>R</i>,<i>R</i>)-Ph-BPE, and NaO<i>t</i>Bu enables the enantioselective coupling of the phenolic hydroxy group with a hydrosilane with moderate to good selectivity factors.