Kinetic Resolution of α‐Hydroxy‐Substituted Oxime Ethers by Enantioselective Cu−H‐Catalyzed Si−O Coupling

A catalyst‐controlled enantioselective alcohol silylation by Cu?H‐catalyzed dehydrogenative Si?O coupling of hydroxy groups α to an oxime ether and simple hydrosilanes is reported. The selectivity factors reached in this kinetic resolution are generally high (s≈50), and these reactions thereby provide reliable access to highly enantioenriched α‐hydroxy‐substituted oxime ethers. The synthetic usefulness of these compounds is also demonstrated.