摘要：KEY WORDS:amination,C-H activation, photo chemistry (反应类型), C(sp2)−N (成键类型), arenes, pyridinium salt (原料), N-arylated product,N-he

转自：康龙化成

Photocatalytic Arene C−H Amination with Aromatic N‑Heterocyclic Radicals

Minxu Shi, Lu Wang, Lei Bao, Tianyu Wang, Nicholas Su, Xiaoping Chen, and Xiaheng Zhang*

School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study,

University of Chinese Academy of Sciences, Hangzhou 310024, P. R. China.

—ACS Catal. 2025, 15, 16863−16872.

Recommended by Yuting Gao_MC3

KEY WORDS: amination,C-H activation, photo chemistry (反应类型), C(sp2)−N (成键类型), arenes, pyridinium salt (原料), N-arylated product,N-heterocycles (产物)

ABSTRACT: Arene C−H amination represents one of the most appealing and efficient strategies for the synthesis of a diverse range of functionalized aromatic amines. Here, Pro. Xiaheng Zhang’sgroup describes a general approach toward arene C−H amination, which leverages the unique chemistry of photocatalytically generated aromatic N-heterocyclic radicals via a homolytic aromatic substitution mechanism. The broad scope of this reaction renders this technique a powerful tool to streamline the preparation of various medicinally relevant N-arylated heterocycles, enabling late-stage modification of structurally diverse conjugated arenes, drugs, and polymers. Finally, a computational study reveals that the origin of N-site selectivity is postulated to be associated with the localized radical character at the nitrogen center.

Development of arene C−H amination with aromatic N-heterocyclic radicals

Scope of aromatic nitrogen heterocycles

Scope of the complex (hetero)arenes

Mechanism

The group of Pro. Xiaheng Zhanghas developed a novel and efficient photocatalytic method for the C−H amination of arenes facilitated by aromatic N -heterocyclic radicals, representing a new radical approach to afford structurally diverse N-arylated heterocycles, which complements existing methods. With its broad substrate applicability, ranging from simple aromatics to sophisticated molecules such as complex conjugated arenes, pharmaceuticals, and polystyrene, this methodology holds promise for inspiring advancements in C(sp2)−N bond forming reactions.

来源：新浪财经