Rhodium‐Catalysed Asymmetric Arylation of Pyridylimines

Abstract

The catalytic asymmetric arylation of pyridylimines was developed. A range of pyridylimines reacted with arylboronic acids under rhodium catalysis to produce pyridine‐incorporating chiral diarylmethylamines in 46% to 99% yield with 90:10 to 99.5:0.5 er, thus providing a method for the preparation of these important chiral pharmacophores.

Nickel-Catalyzed Enantioselective Reductive Arylation and Heteroarylation of Aldimines via an Elementary 1,4-Addition

“…Developing efficient methods for stereoselective synthesis of these chiral amines has attracted long-lasting interest among synthetic chemists . Among these methods, metal-catalyzed asymmetric addition of benchtop-stable aryl boron reagents to imines has been extensively studied and well developed, and most of them use expensive 4d noble metals such as rhodium and palladium owing to efforts of Hayashi, Lin and Xu, Zhang, etc. Mechanistically, these reactions proceed via an elementary 1,2-addition of aryl metals across imines .…”

Rh(II)-Catalyzed C–N Bond Formation Using Enynones and N–H Imines: An Approach to Diarylmethylamines

“…Diarylmethylamines are important frameworks in medicinal chemistry, as they are ubiquitous in the structures of many commercial drugs . Fortunately, several efficient methods have been developed for the preparation of diarylmethylamines.…”

Enantioselective Construction of C3-Multifunctionalization α-Hydroxy-β-amino Pyridines via α-Pyridyl Diazoacetate, Water, and Imines for Drug Hunting

“…Elegant examples of an asymmetric version (Scheme b) for the pyridine C3-position were reported by Tang’s group via Heck reaction between pyridine halides and heterocyclic alkenes. Lin, Jesús, Dou, and others also developed C3-functionalized pyridines via boric acid or borate catalyzed asymmetric addition of pyridylimines. In the past decade, the groups of Zhou, Gao, and Li, respectively, established asymmetric C3-functionalized pyridines via H 2 - or borane-promoted hydrogenation reactions.…”