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

Abstract

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.