康 · 学术 | Reaction of the Day No. 1297

转自：康龙化成

Amination of Aminopyridines via η6‑Coordination Catalysis

JiajiaChen, Yunzhi Lin, Wen-Qiang Wu, Wei-Qiang Hu, Jingkai Xu, and Hang Shi*

Key Laboratory of Precise Synthesis ofFunctional Molecules of Zhejiang Province, School of Science, WestlakeUniversity, Hangzhou 310030 Zhejiang Province, China; Institute of NaturalSciences, Westlake Institute for Advanced Study, Hangzhou 310024 ZhejiangProvince, China;

—J. Am. Chem. Soc.,2024, 146, 22906−22912

Recommended by Rui Jin _ MC5

ABSTRACT: Pyridine,a widespread aromatic heterocycle, features asp2-hybridizednitrogen atom that can readily coordinate to metals, leading to distinctiveachievements in catalysis. In stark contrast, π-coordination of pyridine andderivatives with transition metals is notably scarce, and the involvement ofsuch activation mode in catalysis remains to be developed. Herein, we presentamination reactions of aminopyridines that leverages the reversible πcoordination with a ruthenium catalyst as the arenophilic π acid, rather than relying on theconventional κ-N coordination. Specifically, atransient η6-pyridine complex functions as theelectrophile in the nucleophilic aromatic substitution with amines, providing adiverse array of products via the cleavage of the pyridyl C−N bond. Inaddition, this method can be employed to incorporate chiral amines and 15N-labeled amines.

Background and This Work

Selected Examples of Catalytic Aminationof 2-Aminopyridines and Extended Applications

（转自：康龙化成）