Photoredox Hydroacylative Dearomatization of Indoles with Aromatic Carboxylic Acids

Herein we reported for the first time a photocatalytic dearomative hydroacylation reaction of electron‐deficient indoles with readily available aromatic acids through a phosphoranyl radical‐assisted deoxygenative process. A range of racemic and optically active 2‐acylindoline derivatives were obtained in good yields (up to 94%) with good diastereoselectivity. The synthetic robustness is highlighted by the enantioselective dearomatization of indoles and the late‐stage modification of natural products and pharmaceutical molecules. This protocol features broad substrate scope and mild reaction conditions, providing a reliable entry to developing deoxygenative strategies in dearomatization reactions. Preliminary mechanistic studies and DFT calculations suggest that a Giese‐type radical addition pathway should be involved.