摘要：Shuyang Liu, Ziyu Gan, Min Jiang, Qian Liao, Yusheng Lu, HongyaoWang, Zhiyan Xue, Ziyang Chen, YongqiangZhang, Xiaobo Yang,Chunyin

转自：康龙化成

Selective Arene Photonitrationvia Iron-Complex β‑Homolysis

Shuyang Liu, Ziyu Gan, Min Jiang, Qian Liao, Yusheng Lu, HongyaoWang, Zhiyan Xue, Ziyang Chen, YongqiangZhang, Xiaobo Yang,Chunying Duan, and Yunhe Jin*

Shuyang Liu, Ziyu Gan, Qian Liao, Yusheng Lu, HongyaoWang, Zhiyan Xue, Ziyang Chen, YongqiangZhang, Yunhe Jin− State Key Laboratory of Fine Chemicals, School of Chemistry, DalianUniversity of Technology, Dalian 116024, China;

Min Jiang − College of Materials,Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou310036, China;

Xiaobo Yang − Institute of Catalysis forEnergy and Environment, College of Chemistry and Chemical Engineering, ShenyangNormal University, Shenyang 110034, China;

Chunying Duan − State Key Laboratory ofCoordination Chemistry, Nanjing University, Nanjing 210093, China;

—10.1021/jacsau.4c00880

Recommended by Yilong Zhao_MC2

KEYWORDS: Photocatalysis, nitration (反应类型),C(sp2) – N (成键类型), Arene(原料),Fe(NO3)3-9H2O (原料), arene nitration(产物)

ABSTRACT: Nitroaromatics, asan important member and source of nitrogen-containing aromatics, is bringingenormous economic benefits in fields of pharmaceuticals, dyes, pesticides,functional materials, fertilizers, and explosives. Nonetheless, the notoriouslypolluting nitration industry, which suffers from excessive discharge of fumesand waste acids, poor functional group tolerance, and tremendous purificationdifficulty, renders mild, efficient, and environmentally friendly nitration aformidable challenge. Herein, we develop a visible-light-driven biocompatiblearene C−H nitration strategy with good efficiency and regioselectivity,marvelous substrate applicability and functional group tolerance, and wideapplication in scale-up synthesis, total synthesis, and late-stagefunctionalization. A nitrylradical delivered through unusual β-homolysis of a photoexcitedferric-nitrate complex is proposed to be the key nitrification reagent in thissystem.

Previous protocols for arene nitration

Approaches for generating nitryl radicals

Selected substrate scope

General design plan for the mechanisms ofarene photonitration viairon-complex β-homolysis

Summary and Comments

Prof.Jin and co-workers have developed a visible-light-initiated biocompatible arene C−Hnitration with high efficiency and regioselectivity,marvelous functional group tolerance such as trifluoromethyl,acetyl, ester, and cyanogroups etc. and substrate suitability, and wide application in scale-upsynthesis, total synthesis, and late-stage modification, which demonstrates itspractical and potential for Lab and industrial application.

来源：新浪财经