Homogeneous Catalytic Reduction of Aromatic Nitro-Compounds by Hydrogen Transfer

Abstract

In the presence of noble metal salts, indoline reduced aromatic nitro-compounds to the corresponding aromatic amines under mild reaction conditions.

Photochemically Engineering the Metal–Semiconductor Interface for Room‐Temperature Transfer Hydrogenation of Nitroarenes with Formic Acid

“…Alternatively, nitroarene compounds can be reduced to aromatic amines by "extracting" hydrogen from hydrogen-donor molecules, that is, transfer hydrogenation. [14][15][16][17][18][19][20] Among the available hydrogen donors, [21][22][23] FA, which may be derived from biomass with low toxicity and high stability, is an abundant and cheap hydrogen source for safe hydrogen usage and storage. [24][25][26] The only byproduct of dehydrogenation reaction of FA, CO 2 , could be regenerated to FA by chemical or biological routes in large quantities, [24,25] completing the sustainable cycles for the potential use of FA as hydrogen source.…”

Chemoselective Transfer Hydrogenation to Nitroarenes Mediated by Cubane‐Type Mo3S4 Cluster Catalysts

“…[4] A crucial issue for the general application of catalysts for nitro reduction is selectivity. [7,8] Hence, a wide variety of organometallic catalysts based on Pd, [7] Ru, [7][8][9] Rh, [7] Co, [10] Cu, [10] and even Fe [11] have been described. Recently, Corma and co-workers demonstrated that Au-based catalysts show high selectivity for the reduction of the nitro arenes.…”

Utilization of a Hydrogen Source from Renewable Lignocellulosic Biomass for Hydrogenation of Nitroarenes

“…Nitroarene (1) is hydrogenated to nitrosoarene (5) by the iridium hydride complex and proton with release of one molecular water. [6d,23] Then a sequent hydrogenation of 5 leads to hydroxylamine (6), which under-goes a followed hydrogenation with release of the second water to afford the desired arylamine (2, Path A). An equilibrium is existed between 2 and the condensation intermediate 4.…”

“…[2,3] On the other hand, the combinations of protons with hydride reagents or electron donors, and other in-situ generated hydrogen sources by hydrogen transformation were also well developed ( Figure 1B). [2,[4][5][6] Exploring of hydrogen source from renewable resource for direct hydrogenation reactions, such as glucose in alkaline solution, had been studied since 1860s ( Figure 1C). [7a] In these reactions, more than stoichiometric amounts of glucose and base were required.…”

“…[22,23] Hydrogenation of nitroarenes is one of the most classic methods for preparation of arylamines by utilization of H 2 [23,24] and other hydrogen sources as mentioned above. [2,[4][5][6][7][10][11] Herein, we report the utilization of hydrogen source from renewable lignocellulosic biomass, one of the most abundant renewable source in nature, for a hydrogenation reaction. The hydrogenation is demonstrated by reduction of nitroarenes to corresponding arylamines (Scheme 1).…”