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Chemoselective Transfer Hydrogenation of Nitroarenes with Ammonia Borane Catalyzed by Copper N‐heterocyclic Carbene Complexes
Chinese Journal of Chemistry ( IF 5.4 ) Pub Date : 2024-03-26 , DOI: 10.1002/cjoc.202400069
Hui Zhou 1 , Hongmei Jiao 1 , Xing Lu 1 , Yuanyuan Gao 1 , Zhiqiang Ren 1 , Haojie Ma 1 , Yuqi Zhang 1 , Bo Han 1
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Comprehensive SummaryHerein, we present a method for the homogeneous hydrogenation of nitroarenes to produce anilines using low catalyst loading (1 mo%) of copper N‐heterocyclic carbene complexes as the catalyst and ammonia borane as the source of hydrogen. A wide range of nitroarenes, featuring diverse functional groups, were selectively transformed into their corresponding primary aromatic amines with high yields. This process can be readily scaled up and exhibits compatibility with various sensitive functional groups, including halogen, trifluoromethyl, aminomethyl, alkenyl, cyano, ester, amide, and hydroxyl. Notably, this catalytic methodology finds application in the synthesis of essential drug compounds. Mechanistic investigations suggest that the in‐situ‐generated Cu‐H species may serve as active intermediates, with reduction pathways involving species such as azobenzene, 1,2‐diphenylhydrazine, nitrosobenzene, and N‐phenylhydroxylamine.

中文翻译:

铜N-杂环卡宾配合物催化氨硼烷化学选择性转移氢化硝基芳烃

综合总结在此,我们提出了一种使用低催化剂负载量(1 mo%)铜对硝基芳烃均相氢化生产苯胺的方法‐杂环卡宾配合物作为催化剂,氨硼烷作为氢源。各种具有不同官能团的硝基芳烃被选择性地转化为相应的芳香伯胺,且产率较高。该过程可以很容易地扩大规模,并表现出与各种敏感官能团的兼容性,包括卤素、三氟甲基、氨甲基、烯基、氰基、酯、酰胺和羟基。值得注意的是,这种催化方法可用于基本药物化合物的合成。机制研究表明原位生成的 Cu-H 物质可以作为活性中间体,还原途径涉及偶氮苯、1,2-二苯肼、亚硝基苯和‐苯基羟胺。
更新日期:2024-03-26
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