Aerobic Asymmetric Dehydrogenative Cross‐Coupling between Two CH Groups Catalyzed by a Chiral‐at‐Metal Rhodium Complex

A sustainable C? C bond formation is merged with the catalytic asymmetric generation of one or two stereocenters. The introduced catalytic asymmetric cross‐coupling of two C? H groups with molecular oxygen as the oxidant profits from the oxidative robustness of a chiral‐at‐metal rhodium(III) catalyst and exploits an autoxidation mechanism or visible‐light photosensitized oxidation. In the latter case, the catalyst serves a dual function, namely as a chiral Lewis acid for catalyzing enantioselective enolate chemistry and at the same time as a visible‐light‐driven photoredox catalyst.