Anilines as C-Nucleophiles in Ir-Catalyzed Intramolecular Asymmetric Allylic Substitution Reactions.

Anilines generally act as N-nucleophiles in transition-metal-catalyzed allylic substitution reactions. In this paper, a highly enantioselective intramolecular Friedel-Crafts-type allylic alkylation of aniline derivatives was realized by using an iridium catalyst derived from [Ir(cod)Cl]2 and (Ra )-BHPphos. Various tetrahydroisoquinilin-5-amines were obtained in moderate to good yields, excellent enantioselectivity and regioselectivity under mild reaction conditions. BHPphos=N-benzhydryl-N-phenyldinaphthophosphoramidite.