Catalytic reduction of nitroarenes to the corresponding anilines is a crucial reaction in the fine and bulk chemical industry, however, the control of chemoselectivity remains enormous challenges when additional reducible groups exist in the same molecule of nitroarenes. Herein, we summarize the breakthroughs over the recent 10 years in this review, especially the recent 5 years, which focus on the selectivity control of catalytic reduction of nitroarenes that bear other reducible functional groups, including nitrostyrene, halogenated nitrobenzene, nitrobenzaldehyde, nitroacetophenone, nitrobenzonitrile, and nitrophenylacetylene. We mainly discuss the origin of the catalytic selectivity, which are classified as natural selectivity, intrinsic selectivity, and preferential adsorption. We attempt to discover how the hydrogen sources and metal catalysts affect the catalytic selectivity, and how to design and fabricate efficient catalysts for the selective reduction of -NO₂ group. The selectivity caused by hydrogen sources is assigned as natural selectivity, and it is interesting that the hydrogen source contains protonic active hydrogen has natural selectivity to nitro group. Through analyzing various reported experimental results, we have rendered such a blueprint about the selectivity sequence for diverse hydrogen sources: in some cases, the more protonic active hydrogen in the molecule, the better its natural selectivity towards nitro reduction (N₂H₄·H₂O>HCOOH>NaBH₄, NH₃·BH₃> H₂). Moreover, the catalytic selectivity of metal catalysts for reducing nitroarenes containing other reducible groups depends on two central factors: intrinsic selectivity and preferential adsorption. Various approaches to improve the selectivity of metal catalysts have been discussed, including the adjustment of the metal-support interactions, confinement of metals in the pores of the supports, modification of metals with non-metallic elements (N, S, P, etc.), construction of bimetallic alloys or intermetallics, formation of single-atom catalysts, and so on. This review will further strengthen the understanding of the selectivity for the reduction of substituted nitroarenes and provide guidance for the design and preparation of highly efficient and selective metal catalysts.

硝基芳烃催化还原为相应的苯胺是精细化工和大宗化工行业的关键反应，然而，当同一硝基芳烃分子中存在额外的可还原基团时，化学选择性的控制仍然是巨大的挑战。在此，我们总结了本综述近 10 年，特别是近 5 年的突破，重点是催化还原带有其他可还原官能团的硝基芳烃的选择性控制，包括硝基苯乙烯、卤代硝基苯、硝基苯甲醛、硝基苯乙酮、硝基苯甲腈, 和硝基苯乙炔。我们主要讨论催化选择性的起源，催化选择性分为自然选择性、本征选择性和优先吸附。₂组。由氢源引起的选择性被归类为自然选择性，有趣的是氢源含有质子活性氢对硝基具有天然选择性。通过对各种报道的实验结果的分析，我们得出了这样一个关于不同氢源选择性顺序的蓝图：在某些情况下，分子中的质子活性氢越多，其对硝基还原（N ₂ H ₄ ·H ₂ O>HCOOH>NaBH ₄ , NH ₃ ·BH ₃ > H ₂）。此外，用于还原含有其他可还原基团的硝基芳烃的金属催化剂的催化选择性取决于两个核心因素：固有选择性和优先吸附。已经讨论了提高金属催化剂选择性的各种方法，包括调节金属-载体相互作用、将金属限制在载体孔中、用非金属元素（N、S、P 等）改性金属。 )、双金属合金或金属间化合物的构建、单原子催化剂的形成等。该综述将进一步加强对取代硝基芳烃还原选择性的理解，并为高效选择性金属催化剂的设计和制备提供指导。