Asymmetric Synthesis of Dialkyl Carbinols by Ni‐Catalyzed Reductive‐Oxidative Relay of Distinct Alkenes

Abstract Enantioenriched unsymmetric dialkyl carbinol derivatives are of importance in natural products, bioactive molecules, and functional organic materials. However, the catalytic asymmetric synthesis of dialkyl carbinol derivatives remains challenging due to the similar steric and electronic properties of two alkyl substituents. Herein, an unprecedented synthesis of chiral dialkyl carbinol ester derivatives from Ni‐catalyzed reductive‐oxidative relay cross‐coupling of two alkenes is developed for the first time. The reaction features the use of enol esters and unactivated alkenes as two different alkyl equivalents to undergo head‐to‐tail and enantioselective alkyl‐alkyl cross‐coupling. The reaction undergoes two‐electron reduction and single electron oxidation in the presence of both reductants and oxidants. The use of an allyl bromide as single electron acceptor is crucial for the success of this non‐trivial asymmetric cross‐coupling, providing a new reaction mode for asymmetric alkyl‐alkyl bond‐forming event in the absence of stoichiometric alkyl electrophiles.