Kinetic Resolution\nof BINOLs and Biphenols by Atroposelective,\nCu–H-Catalyzed Si–O Coupling with Hydrosilanes

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