Benzimidazole derivatives have wide-spectrum biological activities and pharmacological effects, but remain challenging to be produced from biomass feedstocks. Here, we report a green hydrogen transfer strategy for the efficient one-pot production of benzimidazoles from a wide range of bio-alcohols and o-nitroanilines enabled by cobalt nitride species on hierarchically porous and recyclable nitrogen-doped carbon catalysts (Co/CN_x-T, T denotes the pyrolysis temperature) without using an external hydrogen source and base additive. Among the tested catalysts, Co/CN_x-700 exhibited superior catalytic performance, furnishing 2-substituted benzimidazoles in 65%–92% yields. Detailed mechanistic studies manifest that the coordination between Co²⁺ and N with appropriate electronic state on the porous nitrogen-doped carbon having structural defects, as well as the remarkable synergetic effect of Co/N dual sites contribute to the pronounced activity of Co/CN_x-700, while too high pyrolysis temperature may cause the breakage of the catalyst Co-N bond to lower down its activity. Also, it is revealed that the initial dehydrogenation of bio-alcohol and the subsequent cyclodehydrogenation are closely correlated with the hydrogenation of nitro groups. The catalytic hydrogen transfer-coupling protocol opens a new avenue for the synthesis of N-heterocyclic compounds from biomass.

苯并咪唑衍生物具有广谱的生物活性和药理作用，但从生物质原料生产仍然具有挑战性。在这里，我们报告了一种绿色氢转移策略，用于在分级多孔和可回收的氮掺杂碳催化剂（Co/CN _x -T，T 表示热解温度），不使用外部氢源和碱添加剂。在测试的催化剂中，Co/CN _x -700 表现出优异的催化性能，以 65%–92% 的收率提供 2-取代苯并咪唑。详细的机理研究表明，Co ²⁺和N在具有结构缺陷的多孔氮掺杂碳上具有适当的电子态，以及Co/N双位点的显着协同效应有助于Co/CN _x -700的显着活性，而过高的热解温度可能导致催化剂Co-N键的断裂以降低其活性。此外，还揭示了生物醇的初始脱氢和随后的环化脱氢与硝基的氢化密切相关。催化氢转移偶联方案为从生物质中合成N-杂环化合物开辟了一条新途径。