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

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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/CNx-T, T denotes the pyrolysis temperature) without using an external hydrogen source and base additive. Among the tested catalysts, Co/CNx-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/CNx-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.

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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.

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  1. State Key Laboratory Breeding Base of Green Pesticide & Agricultural Bioengineering, Key Laboratory of Green Pesticide & Agricultural Bioengineering, Ministry of Education, State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for R&D of Fine Chemicals, Guizhou University, Guiyang, 550025, China

    Chuanhui Li, Li-Long Zhang, Hu Li & Song Yang

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  1. Chuanhui Li
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  2. Li-Long Zhang
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  3. Hu Li
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Correspondence to Hu Li or Song Yang.

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

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Li, C., Zhang, LL., Li, H. et al. Cobalt nitride enabled benzimidazoles production from furyl/aryl bio-alcohols and o-nitroanilines without an external H-source. Front. Chem. Sci. Eng. 17, 68–81 (2023). https://doi.org/10.1007/s11705-022-2174-y

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