Skeleton‐Reorganizing Coupling Reactions of Cycloheptatriene and Cycloalkenones with Amines

Abstract Skeletal reorganization reactions have emerged as an intriguing tool for converting readily available compounds into complicated molecules inaccessible by traditional methods. Herein, we report a unique skeleton‐reorganizing coupling reaction of cycloheptatriene and cycloalkenones with amines. In the presence of Rh/acid catalysis, cycloheptatriene can selectively couple with anilines to deliver fused 1,2‐dihydroquinoline products. Mechanistic studies indicate that the retro‐Mannich type ring‐opening and subsequent intramolecular Povarov reaction account for the ring reorganization. Our mechanistic studies also revealed that skeleton‐reorganizing amination between anilines and cycloalkenones can be achieved with acid. The synthetic utilization of this skeleton‐reorganizing coupling reaction was showcased with a gram‐scale reaction, synthetic derivatizations, and the late‐stage modification of commercial drugs.