Construction of Vicinal Quaternary Carbon Stereocenters Through Diastereo‐ and Enantioselective Oxidative 1,6‐Conjugate Addition

Abstract The asymmetric construction of vicinal quaternary carbon stereocenters with at least one moiety in acyclic systems is a formidable challenge. We disclose a solution involving diastereo‐ and enantioselective oxidative 1,6‐conjugate addition. The practical asymmetric cross‐dehydrogenative coupling of 2,2‐diarylacetonitriles and diverse α‐substituted cyclic 1,3‐dicarbonyls proceeds, for vicinal quaternary carbon stereocenters with one center in acyclic systems, in excellent yields and stereoselectivities. The generality of the approach is further demonstrated by the stereoselective creation of vicinal quaternary carbon stereocenters with both centers in acyclic systems using acyclic β‐ketoesters as coupling partners. Computational studies elucidate the origins of both diastereo‐ and enantioselectivity.