Cobalt‐Catalyzed Desymmetrizing Hydrogenation of Cyclic Anhydrides

Achieving general asymmetric catalytic manifolds that accommodate broad substrate diversity remains a long‐standing and highly sought‐after goal in synthetic chemistry. Herein, we report an efficient cobalt‐catalyzed desymmetric hydrogenation of structurally diverse cyclic 1,2‐ and 1,3‐diacid anhydrides, enabling access to pharmaceutically relevant chiral γ ‐ and δ ‐lactones with broad substrate scope and excellent enantioselectivity (up to 99% ee). The reaction is readily scalable, as demonstrated by gram‐scale synthesis of several representative products. Notably, this 3d‐metal catalytic platform represents a rare example that outperforms platinum‐group‐metal‐based counterparts in both generality and stereoselectivity. DFT studies identify a catalytically active d 7 Co(II) dihydride complex with an outer‐sphere hydride transfer mechanism, wherein a relatively flexible chiral pocket underlies the broad substrate compatibility of this catalytic system.