Chemo-, site-selective reduction of nitroarenes under blue-light, catalyst-free conditions

• Published in: Chinese chemical letters Vol. 33; no. 5; pp. 2420 - 2424
• Main Authors: Wang, Bin, Ma, Jiawei, Ren, Hongyuan, Lu, Shuo, Xu, Jingkai, Liang, Yong, Lu, Changsheng, Yan, Hong
• Format: Journal Article
• Language: English
• Published: NEW YORK Elsevier B.V 01.05.2022; Elsevier; State Key Laboratory of Coordination Chemistry,Jiangsu Key Laboratory of Advanced Organic Materials,School of Chemistry and Chemical Engineering,Nanjing University,Nanjing 210023,China
• Subjects: Catalyst-free; Chemistry; Chemistry, Multidisciplinary; Nitroarenes; Photoinduced; Physical Sciences; Reduction; Science & Technology; Selective; Transborylation; Reduction; Nitroarenes; Catalyst-free; Selective; Transborylation; Photoinduced; GOLD; ACID; HIGHLY EFFICIENT; ATOM; AROMATIC NITRO-COMPOUNDS; NITROBENZENE; NANOPARTICLES; NITROAROMATICS; CHEMOSELECTIVE HYDROGENATION
• ISSN: 1001-8417; 1878-5964
• DOI: 10.1016/j.cclet.2021.11.023

The tandem reaction of photoinduced double hydrogen-atom transfer and deoxygenative transborylation for chemo- and site-selective reduction of nitroarenes into aryl amines under catalyst-free, room temperature conditions was disclosed in excellent yields. In this reaction, isopropanol (iPrOH) was used as hydrogen donor and tetrahydroxydiboron [B2(OH)4] as deoxygenative reagent with green, cheap, and commercially available credentials. In particular, a wide range of reducible functional groups such as halogen (-Cl, -Br and even -I), alkenyl, alkynyl, aldehyde, ketone, carboxyl, and cyano are all tolerated. Moreover, the reaction preferentially reduces the nitro group at the electron-deficient site over another nitro group in the same molecule. A detailed mechanistic investigation in combination of experiments and theoretical calculations gave a reasonable explanation for the reaction pathway. [Display omitted] The tandem reaction of photoinduced double hydrogen-atom transfer and deoxygenative transborylation for chemo- and site-selective reduction of nitroarenes into aryl amines under catalyst-free, room temperature conditions was disclosed in excellent yields. A detailed mechanistic investigation in combination of experiments and theoretical calculations gave a reasonable explanation for the reaction pathway.