Rh‐Catalyzed Chemodivergent Parallel Kinetic Resolution and Desymmetrization of Enynes and Dienynes with Acrylamides

ABSTRACT Catalytic enantioselective synthesis of structurally diverse 3D molecules remains a central challenge in organic chemistry. Intermolecular chemodivergent parallel kinetic resolution (PKR) of racemic substrates through C─C bond formation using a single catalyst to yield distinct products is rare. Here, we report Rh‐catalyzed chemodivergent PKR of racemic 1,6‐enynes with α‐fluoroacrylamides or mixtures of different acrylamides, proceeding via [2+2+2] cycloaddition and C–H alkylation to afford structurally and stereochemically distinct products with high selectivity under mild conditions. Additionally, substituent‐dependent enantioselective desymmetrization of symmetric dienynes was achieved. Computational studies revealed that, depending on the stereochemistry of the 1,6‐enyne, steric repulsion between the ligand and the enyne favors a compact C–H activation transition state, whereas its absence favors a C═C insertion transition state involving a smaller bond dissociation energy. These findings establish a versatile catalytic platform for the selective generation of 3D molecular complexity, advancing diversity‐oriented synthesis from racemic or symmetric precursors.