Gearing Effects on <i>N</i>-9-Anth-PyBidine-Cu(OAc)₂-Catalyzed Asymmetric Direct Haloimidation Reactions of Alkylidenemalononitriles

A newly developed <i>N</i>-9-anthranylmethyl bis(imidazolidine)pyridine (<i>N</i>-9-Anth-PyBidine)-Cu(OAc)₂ complex catalyzed asymmetric haloimidation reactions of alkylidenemalononitriles with <i>N</i>-bromosuccinimide and <i>N</i>-chlorosuccinimide, employing the succinimide moiety directly as a copper-bound nucleophile. The anthranyl substituent showed a gearing effect that produced a well-organized asymmetric sphere involving the <i>N</i>-H proton of the imidazolidine ring in the ligand. The gearing effect afforded hydrogen bonding-assisted copper-catalyzed haloimidation reactions with high enantioselectivity.