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

作　　者：Chuanhui Li Li-Long Zhang Hu Li Song Yang 

机构地区：[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

出　　处：《Frontiers of Chemical Science and Engineering》2023年第1期68-81,共14页化学科学与工程前沿（英文版）

基　　金：supported by the National Natural Science Foundation of China(Grant No.21908033);Guizhou Provincial S&T Project(Grant No.ZK[2022]011,2018[4007]);Fok Ying-Tong Education Foundation(Grant No.161030).

摘　　要：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 Co^(2+)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.

关 键 词：biomass conversion furanic compounds BENZIMIDAZOLES hydrogen transfer bifunctional catalysis 

分 类 号：O62[理学—有机化学]