Catalytic Asymmetric Cascade Dearomatization of Indoles via a Photoinduced Pd‐Catalyzed 1,2‐Bisfunctionalization of Butadienes

Photoinduced Pd‐catalyzed bisfunctionalization of butadienes with a readily available organic halide and a nucleophile represents an emerging and attractive method to assemble versatile alkenes bearing various functional groups at the allylic position. However, enantiocontrol and/or diastereocontrol in the C‐C or C‐X bond‐formation step have not been solved due to the open‐shell process. Herein, we present a cascade asymmetric dearomatization reaction of indoles via photoexcited Pd‐catalyzed 1,2‐biscarbonfunctionalization of 1,3‐butadienes, wherein asymmetric control on both the nucleophile and electrophile part is achieved for the first time in photoinduced bisfunctionalization of butadienes. This method delivers structurally novel chiral spiroindolenines bearing two contiguous stereogenic centers with high diastereomeric ratios (up to >20:1 dr) and good to excellent enantiomeric ratios (up to 97:3 er). Experimental and computational studies of the mechanism have confirmed a radical pathway involving excited‐state palladium catalysis. The alignment and non‐covalent interactions between the substrate and the catalyst were found to be essential for stereocontrol.