Gold‐Catalyzed Arylative Cope Rearrangement

Cope rearrangements have garnered significant attention owing to their ability to undergo structural reorganization in stereoselective manner. While substantial advances have been achieved over decades, these rearrangements remained applicable exclusively to parent 1,5‐hexadienes. Herein, we disclose the gold‐catalyzed arylative Cope rearrangement of 1,6‐heptadienes via a cyclization‐induced [3,3]‐rearrangement employing ligand‐enabled gold redox catalysis. Detailed mechanistic investigations including several control experiments, cross‐over experiment, HRMS analysis, 31P NMR and DFT studies have been performed to underpin the mechanism. Reported herein is the arylative Cope rearrangement of 1,6‐heptadienes facilitated by ligand‐enabled redox gold catalysis. Unlike the classical Cope rearrangement involving 1,5‐hexadienes, a cyclization‐induced [3,3]‐rearrangement of 1,6‐heptadienes using the merger of π‐activation and cross‐coupling reactivity, has been achieved.