New Applications of Chiral N-Heterocyclic Carbene Ligands
Created on 2025.08.15
In 1991, the isolation and characterization of N-heterocyclic carbenes (NHCs) by American chemist Anthony J. Arduengo triggered the rapid development of research on N-heterocyclic carbenes. However, the development of chiral N-heterocyclic carbene ligands was once limited by issues such as a single structural type and low enantioselectivity. In recent years, the research group of Shi proposed the concept of "induced fit catalysis" and developed the original chiral N-heterocyclic carbene (NHC) ligand series ANIPE and SIPE, breaking through the traditional design concepts. In addition, the research group of Fan also developed new C1-symmetric chiral NHC ligands with adjustable structures. In terms of applications, chiral N-heterocyclic carbene ligands are widely used in metal-catalyzed asymmetric reactions, such as asymmetric coupling, addition, C-H functionalization, and alkene functionalization reactions. Recently, the team of Wang from Ocean University of China and Zhao from Shanghai Institute of Organic Chemistry achieved nickel-catalyzed asymmetric reductive cross-coupling reactions between aldehydes and four-membered heterocyclic alkenes under the regulation of NHC ligands, which can efficiently and highly selectively construct bioisosteres of α-hydroxyketones. Mechanistic studies revealed that the reaction activity driven by ring tension and ligand regulation jointly control the chemoselectivity, regioselectivity, and stereoselectivity.
Literature details
Authors: Mingshuai Zhang, Meihong Luo, Gang Zhao,* and Hongyu Wang*
Title: Nickel-Catalyzed Regioselective and Enantioselective Olefin–Aldehyde Cross-Couplings Toward Acyloin Isosteres
DOI: 10.1002/anie.202510690