New Applications of Chiral N-Heterocyclic Carbene Ligands
Created on 08.15
In 1991, theisolation and characterization of N-heterocyclic carbenes (NHCs) by Americanchemist Anthony J. Arduengo triggered the rapid development of research onN-heterocyclic carbenes. However, the development of chiral N-heterocycliccarbene ligands was once limited by issues such as a single structural type andlow enantioselectivity. In recent years, the research group of Shi proposed theconcept of "induced fit catalysis" and developed the original chiralN-heterocyclic carbene (NHC) ligand series ANIPE and SIPE, breaking through thetraditional design concepts. In addition, the research group of Fan alsodeveloped new C1-symmetric chiral NHC ligands with adjustable structures. Interms of applications, chiral N-heterocyclic carbene ligands are widely used inmetal-catalyzed asymmetric reactions, such as asymmetric coupling, addition,C-H functionalization, and alkene functionalization reactions. Recently, theteam of Wang from Ocean University of China and Zhao from Shanghai Institute ofOrganic Chemistry achieved nickel-catalyzed asymmetric reductive cross-couplingreactions between aldehydes and four-membered heterocyclic alkenes under theregulation of NHC ligands, which can efficiently and highly selectivelyconstruct bioisosteres of α-hydroxyketones. Mechanistic studies revealed thatthe reaction activity driven by ring tension and ligand regulation jointlycontrol the chemoselectivity, regioselectivity, and stereoselectivity.
Literature details
Authors：Mingshuai Zhang, Meihong Luo, Gang Zhao,* andHongyu Wang*
Title：Nickel-Catalyzed Regioselective andEnantioselective Olefin–Aldehyde Cross-Couplings Toward Acyloin Isosteres
DOI：10.1002/anie.202510690