Cobalt nitride enabled benzimidazoles production from furyl/aryl bio-alcohols and o-nitroanilines without an external H-source

Abstract

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.

Keywords

biomass conversion / furanic compounds / benzimidazoles / hydrogen transfer / bifunctional catalysis

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Grant No. 21908033), Guizhou Provincial S&T Project (Grant No. ZK[2022]011, 2018[4007]), and Fok Ying-Tong Education Foundation (Grant No. 161030). The authors thank Dr. Sudarsanam Putla (Indian Institute of Technology Hyderabad) for his help in improving the English writing of this manuscript.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2174-y and is accessible for authorized users.

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