Selective Arene Photonitration via Iron-Complex β-Homolysis

Shuyang Liu; Ziyu Gan; Min Jiang; Qian Liao; Yusheng Lu; Hongyao Wang; Zhiyan Xue; Ziyang Chen; Yongqiang Zhang; Xiaobo Yang; Chunying Duan; Yunhe Jin

doi:10.1021/jacsau.4c00880

Selective Arene Photonitration via Iron-Complex β-Homolysis

JACS Au. 2024 Nov 21;4(12):4899-4909. doi: 10.1021/jacsau.4c00880. eCollection 2024 Dec 23.

Authors

Shuyang Liu¹, Ziyu Gan¹, Min Jiang², Qian Liao¹, Yusheng Lu¹, Hongyao Wang¹, Zhiyan Xue¹, Ziyang Chen¹, Yongqiang Zhang¹, Xiaobo Yang³, Chunying Duan⁴, Yunhe Jin¹

Affiliations

¹ State Key Laboratory of Fine Chemicals, School of Chemistry, Dalian University of Technology, Dalian 116024, China.
² College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036, China.
³ Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China.
⁴ State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, China.

Abstract

Nitroaromatics, as an important member and source of nitrogen-containing aromatics, is bringing enormous economic benefits in fields of pharmaceuticals, dyes, pesticides, functional materials, fertilizers, and explosives. Nonetheless, the notoriously polluting nitration industry, which suffers from excessive discharge of fumes and waste acids, poor functional group tolerance, and tremendous purification difficulty, renders mild, efficient, and environmentally friendly nitration a formidable challenge. Herein, we develop a visible-light-driven biocompatible arene C-H nitration strategy with good efficiency and regioselectivity, marvelous substrate applicability and functional group tolerance, and wide application in scale-up synthesis, total synthesis, and late-stage functionalization. A nitryl radical delivered through unusual β-homolysis of a photoexcited ferric-nitrate complex is proposed to be the key nitrification reagent in this system.