荒井 孝義

A newly developed N-9-anthranylmethyl bis(imidazolidine)pyridine (N-9-Anth-PyBidine)-Cu(OAc)2 complex catalyzed asymmetric haloimidation reactions of alkylidenemalononitriles with N-bromosuccinimide and N-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 N-H proton of the imidazolidine ring in the ligand. The gearing effect afforded hydrogen bonding-assisted copper-catalyzed haloimidation reactions with high enantioselectivity.

Abstract In a tris(pentafluorophenyl)borane [B(C₆F₅)₃]‐catalyzed reaction of alkenes with cyanogen halides (XCN), BrCN proceeds in a cyanation/bromination manner, in which a cationic CN character is realized. The reaction using ICN switched the mode to iodination/cyanation for enamide substrates and electron‐enriched styrenes. The origin of the iodination/cyanation is the B(C₆F₅)₃‐enhanced σ‐hole generated on ICN.