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

Org Lett. 2024 Dec 20;26(50):10678-10683. doi: 10.1021/acs.orglett.4c03405. Epub 2024 Dec 3.

Abstract

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.