Phosphine-Catalyzed Divergent [4+3] Domino Annulations of CF3-Containing Imines with MBH Carbonates: Construction of Perfluoroalkylated Benzazepines.

Phosphine-catalyzed divergent [4+3] domino annulations of fluorinated imidoyl chlorides with MBH carbonates were developed. Two classes of perfluoroalkylated benzazepines were obtained in moderate to good yields via an interesting dearomatization/rearomatization sequence. Remarkably, the fluorinated imidoyl chlorides could be utilized for the first time as a new four-atom building block in phosphine catalysis. Moreover, the proposed mechanism is supported by capturing the intermediate.