Radical‐Based Enantioconvergent Reductive Couplings of Racemic Allenes and Aldehydes

Abstract Transition metal‐catalyzed radical‐based enantioconvergent reactions have become a powerful strategy to synthesize enantiopure compounds from racemic starting materials. However, existing methods primarily address precursors with central chirality, neglecting those with axial chirality. Herein, we describe the enantioconvergent reductive coupling of racemic allenes with aldehydes, facilitated by a photoredox, chromium, and cobalt triple catalysis system. This method selectively affords one product from sixteen possible regio‐ and stereoisomers. The protocol leverages Co III −H mediated hydrogen atom transfer (MHAT) and Cr‐catalyzed radical‐polar crossover for efficient stereoablation of axial chirality and asymmetric addition, respectively. Supported by mechanistic insights from control experiments, deuterium labeling, and DFT calculations, our approach offers synthetic chemists a valuable tool for creating enantioenriched chiral homoallylic alcohols, promising to advance radical‐based strategies for synthesizing complex chiral molecules.