Cobalt nitride enabled benzimidazoles production from furyl/aryl bio-alcohols and o-nitroanilines without an external H-source
Chuanhui Li, Li-Long Zhang, Hu Li(), Song Yang()
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
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.
Qingyong Zheng and Ya Gao contributed equally to this work.
引用本文:
. [J]. Frontiers of Chemical Science and Engineering, 2023, 17(1): 68-81.
Chuanhui Li, Li-Long Zhang, Hu Li, Song Yang. Cobalt nitride enabled benzimidazoles production from furyl/aryl bio-alcohols and o-nitroanilines without an external H-source. Front. Chem. Sci. Eng., 2023, 17(1): 68-81.
H Li, W Zhao, Z Fang. Hydrophobic Pd nanocatalysts for one-pot and high-yield production of liquid furanic biofuels at low temperatures. Applied Catalysis B: Environmental, 2017, 215 : 18– 27 https://doi.org/10.1016/j.apcatb.2017.05.039
2
H Li, Y Li, Z Fang, R L Jr Smith. Efficient catalytic transfer hydrogenation of biomass-based furfural to furfuryl alcohol with recycable Hf-phenylphosphonate nanohybrids. Catalysis Today, 2019, 319 : 84– 92 https://doi.org/10.1016/j.cattod.2018.04.056
3
C Xu, E Paone, D Rodriguez-Padro, R Luque, F Mauriello. Recent catalytic routes for the preparation and the upgrading of biomass derived furfural and 5-hydroxymethylfurfural. Chemical Society Reviews, 2020, 49( 13): 4273– 4306 https://doi.org/10.1039/D0CS00041H
4
J He, H Li, S Shunmugavel, S Yang. Catalytic upgrading of biomass-derived sugars with acidic nanoporous materials: structural role in carbon-chain length variation. ChemSusChem, 2019, 12( 2): 347– 378 https://doi.org/10.1002/cssc.201802113
5
S Campisi, C E Chan-Thaw, L E Chinchilla, A Chutia, G A Botton, K M H Mohammed, N Dimitratos, P P Wells, A Villa. Dual-site-mediated hydrogenation catalysis on Pd/NiO: selective biomass transformation and maintenance of catalytic activity at low Pd loading. ACS Catalysis, 2020, 10( 10): 5483– 5492 https://doi.org/10.1021/acscatal.0c00414
6
R Cioc, M Lutz, E A Pidko, M Crockatt, J K van der Waal, P C A Bruijnincx. Direct Diels-Alder reactions of furfural derivatives with maleimides. Green Chemistry, 2021, 23( 1): 367– 373 https://doi.org/10.1039/D0GC03558K
7
C Marc U J Harm. Preparation of benzene carboxylic acids, esters and anhydrides from furanics. PCT Int. Appl., 2017146581, 2017-08-31
8
H Liu, H Li, N Luo, F Wang. Visible-light-induced oxidative lignin C–C bond cleavage to aldehydes using vanadium catalysts. ACS Catalysis, 2020, 10( 1): 632– 643 https://doi.org/10.1021/acscatal.9b03768
9
F Yan, C Zhao, L Yi, J Zhang, B Ge, T Zhang, W Li. Effect of the degree of dispersion of Pt over MgAl2O4 on the catalytic hydrogenation of benzaldehyde. Chinese Journal of Catalysis, 2017, 38( 9): 1613– 1620 https://doi.org/10.1016/S1872-2067(17)62815-8
10
C Espro, E Paone, F Mauriello, R Gotti, E Uliassi, M L Bolognesi, D Rodríguez-Padrón, R Luque. Sustainable production of pharmaceutical, nutraceutical and bioactive compounds from biomass and waste. Chemical Society Reviews, 2021, 50( 20): 11191– 11207 https://doi.org/10.1039/D1CS00524C
11
Y Li, X Zhou, H Wu, Z Yu, H Li, S Yang. Nanospheric heterogeneous acid-enabled direct upgrading of biomass feedstocks to novel benzimidazoles with potent antibacterial activities. Industrial Crops and Products, 2020, 150 : 112406 https://doi.org/10.1016/j.indcrop.2020.112406
12
H E Hashem, Y E Bakri. An overview on novel synthetic approaches and medicinal applications of benzimidazole compounds. Arabian Journal of Chemistry, 2021, 14( 11): 103418 https://doi.org/10.1016/j.arabjc.2021.103418
13
S Yuk, D H Lee, S Choi, G Doo, D W Lee, H T Kim. An electrode-supported fabrication of thin polybenzimidazole membrane-based polymer electrolyte membrane fuel cell. Electrochimica Acta, 2018, 270 : 402– 408 https://doi.org/10.1016/j.electacta.2018.03.052
14
Z H Zhang, T S Li, J J Li. A highly effective sulfamic acid/methanol catalytic system for the synthesis of benzimidazole derivatives at room temperature. Monatshefte für Chemie, 2007, 138( 1): 89– 94 https://doi.org/10.1007/s00706-006-0566-1
15
R Wang, X X Lu, X Q Yu, L Shi, Y Sun. Acid-catalyzed solvent-free synthesis of 2-arylbenzimidazoles under microwave irradiation. Journal of Molecular Catalysis A: Chemical, 2007, 266( 1-2): 198– 201 https://doi.org/10.1016/j.molcata.2006.04.071
16
C J Zhu, Y Y Wei. An inorganic iodine-catalyzed oxidative system for the synthesis of benzimidazoles using hydrogen peroxide under ambient conditions. ChemSusChem, 2011, 4( 8): 1082– 1086 https://doi.org/10.1002/cssc.201100228
17
P Daw, Y Ben-David, D Milstein. Direct synthesis of benzimidazoles by dehydrogenative coupling of aromatic diamines and alcohols catalyzed by cobalt. ACS Catalysis, 2017, 7( 11): 7456– 7460 https://doi.org/10.1021/acscatal.7b02777
18
R R Putta, S Chun, S B Lee, D C Oh, S Hong. Iron-catalyzed acceptorless dehydrogenative coupling of alcohols with aromatic diamines: selective synthesis of 1,2-disubstituted benzimidazoles. Frontiers in Chemistry, 2020, 8 : 429 https://doi.org/10.3389/fchem.2020.00429
19
L Li, Q Luo, H H Cui, R J Li, J Zhang, T Y Peng. Air-stable ruthenium(II)-NNN pincer complexes for the efficient coupling of aromatic diamines and alcohols to 1H-benzo[d]imidazoles with the liberation of H2. ChemCatChem, 2018, 10( 7): 1607– 1613 https://doi.org/10.1002/cctc.201800017
20
A K Sharma, H Joshi, R Bhaskar, A K Singh. Complexes of (η5-Cp*)Ir(iii) with 1-benzyl-3-phenylthio/selenomethyl-1,3-dihydrobenzoimidazole-2-thione/selenone: catalyst for oxidation and 1,2-substituted benzimidazole synthesis. Dalton Transactions (Cambridge, England), 2017, 46( 7): 2228– 2237 https://doi.org/10.1039/C6DT04271F
21
T Mori, C Ishii, M Kimura. Pd–C catalyzed dehydrogenative oxidation of alcohols to functionalized molecules. Organic Process Research & Development, 2019, 23( 8): 1709– 1717 https://doi.org/10.1021/acs.oprd.9b00207
22
Z J Xu, X L Yu, X X Sang, D W Wang. BINAP-copper supported by hydrotalcite as an efficient catalyst for the borrowing hydrogen reaction and dehydrogenation cyclization under water or solvent-free conditions. Green Chemistry, 2018, 20( 11): 2571– 2577 https://doi.org/10.1039/C8GC00557E
23
Q Guan, Q Sun, L Wen, Z Zha, Y Yang, Z Wang. The synthesis of benzimidazoles via a recycled palladium catalysed hydrogen transfer under mild conditions. Organic & Biomolecular Chemistry, 2018, 16( 12): 2088– 2096 https://doi.org/10.1039/C8OB00323H
24
F Feng, J Ye, Z Cheng, X Xu, Q Zhang, L Ma, C Lu, X Li. Cu-Pd/γ-Al2O3 catalyzed the coupling of multi-step reactions: direct synthesis of benzimidazole derivatives. RSC Advances, 2016, 6( 76): 72750– 72755 https://doi.org/10.1039/C6RA13004F
25
H Yu, K Wada, T Fukutake, Q Feng, S Uemura, K Isoda, T Hirai, S Iwamoto. Effect of phosphorus-modification of titania supports on the iridium-catalyzed synthesis of benzimidazoles. Catalysis Today, 2021, 375 : 410– 417 https://doi.org/10.1016/j.cattod.2020.02.014
26
L Tang, X Guo, Y Yang, Z Zha, Z Wang. Gold nanoparticles supported on titanium dioxide: an efficient catalyst for highly selective synthesis of benzoxazoles and benzimidazoles. Chemical Communications (Cambridge), 2014, 50( 46): 6145– 6148 https://doi.org/10.1039/c4cc01822b
27
S Das, S Mallick, S D Sarkar. Cobalt-catalyzed sustainable synthesis of benzimidazoles by redox-economical coupling of o-nitroanilines and alcohols. Journal of Organic Chemistry, 2019, 84( 18): 12111– 12119 https://doi.org/10.1021/acs.joc.9b02090
28
R R Putta, S Chun, S H Choi, S B Lee, D C Oh, S Hong. Iron(0)-catalyzed transfer hydrogenative condensation of nitroarenes with alcohols: a straightforward approach to benzoxazoles, benzothiazoles, and benzimidazoles. Journal of Organic Chemistry, 2020, 85( 23): 15396– 15405 https://doi.org/10.1021/acs.joc.0c02191
29
T B Nguyen, L Ermolenko, A Al-Mourabi. Sodium sulfide: a sustainable solution for unbalanced redox condensation reaction between o-nitroanilines and alcohols catalyzed by an iron–sulfur system. Synthesis, 2015, 47( 12): 1741– 1748 https://doi.org/10.1055/s-0034-1380134
30
Z Sun, G Bottari, K Barta. Supercritical methanol as solvent and carbon source in the catalytic conversion of 1,2-diaminobenzenes and 2-nitroanilines to benzimidazoles. Green Chemistry, 2015, 17( 12): 5172– 5181 https://doi.org/10.1039/C5GC01040C
31
C Wu, C Y Zhu, K K Liu, S W Yang, Y Sun, K Zhu, Y L Cao, S Zhang, S F Zhuo, M Zhang, Q Zhang, H Zhang. Nano-pyramid-type Co–ZnO/NC for hydrogen transfer cascade reaction between alcohols and nitrobenzene. Applied Catalysis B: Environmental, 2021, 300 : 120288 https://doi.org/10.1016/j.apcatb.2021.120288
32
C H Li, Y Meng, S Yang, H Li. ZIF-67 derived Co/NC nanoparticles enable catalytic leuckart-type reductive amination of bio-based carbonyls to N-formyl compounds. ChemCatChem, 2021, 13( 24): 5166– 5177 https://doi.org/10.1002/cctc.202100977
33
Y Zhang, P Cao, H Y Zhang, G Yin, J Zhao. Cobalt nanoparticles anchoring on nitrogen doped carbon with excellent performances for transfer hydrogenation of nitrocompounds to primary amines and N-substituted formamides with formic acid. Catalysis Communications, 2019, 129 : 105747 https://doi.org/10.1016/j.catcom.2019.105747
34
S Chen, L L Ling, S F Jiang, H Jiang. Selective hydrogenation of nitroarenes under mild conditions by the optimization of active sites in a well defined Co@NC catalyst. Green Chemistry, 2020, 22( 17): 5730– 5741 https://doi.org/10.1039/D0GC01835J
35
P C Poon, Y Wang, W Li, D W S Suen, W W Y Lam, D Z J Yap, L Mehdi, J Qi, X Y Lu, E Y C Wong, C Yang, C W Tsang. Synergistic effect of Co catalysts with atomically dispersed CoNx active sites on ammonia borane hydrolysis for hydrogen generation. Journal of Materials Chemistry A, 2022, 10( 10): 5580– 5592 https://doi.org/10.1039/D1TA09750D
36
T Song, P Ren, Y N Duan, Z Z Wang, X F Chen, Y Yang. Cobalt nanocomposites on N-doped hierarchical porous carbon for highly selective formation of anilines and imines from nitroarenes. Green Chemistry, 2018, 20( 20): 4629– 4637 https://doi.org/10.1039/C8GC01374H
37
M Yuan, Y Long, J Yang, X W Hu, D Xu, Y Y Zhu, Z P Dong. Biomass sucrose-derived cobalt@nitrogen-doped carbon for catalytic transfer hydrogenation of nitroarenes with formic acid. ChemSusChem, 2018, 11( 23): 4156– 4165 https://doi.org/10.1002/cssc.201802163
38
R Q Zhang, A Ma, X Liang, L M Zhao, H Zhao, Z Y Yuan. Cobalt nanoparticle decorated N-doped carbons derived from a cobalt covalent organic framework for oxygen electrochemistry. Frontiers of Chemical Science and Engineering, 2021, 15( 6): 11550– 11560 https://doi.org/10.1007/s11705-021-2104-4
39
F Zhang, J Li, P Liu, H Li, S Chen, Z Li, W Y Zan, J Guo, X M Zhang. Ultra-high loading single CoN3 sites in N-doped graphene-like carbon for efficient transfer hydrogenation of nitroaromatics. Journal of Catalysis, 2021, 400 : 40– 49 https://doi.org/10.1016/j.jcat.2021.05.025
40
L Deng, Z Yang, R Li, B Chen, Q Jia, Y Zhu, Y Xia. Graphene-reinforced metal−organic frameworks derived cobalt sulfide/carbon nanocomposites as efficient multifunctional electrocatalysts. Frontiers of Chemical Science and Engineering, 2021, 15( 6): 1487– 1499 https://doi.org/10.1007/s11705-021-2085-3
41
S Ma, Z Han, K Leng, X Liu, Y Wang, Y Qu, J Bai. Ionic exchange of metal organic frameworks for constructing unsaturated copper single−atom catalysts for boosting oxygen reduction reaction. Small, 2020, 16( 23): 2001384 https://doi.org/10.1002/smll.202001384
42
M Li, L Bai, S J Wu, X D Wen, J Q Guan. Co/CoOx nanoparticles embedded on carbon for efficient catalysis of oxygen evolution and oxygen reduction reactions. ChemSusChem, 2018, 11( 10): 1722– 1727 https://doi.org/10.1002/cssc.201800489
43
T Rui, G P Lu, X Zhao, X Cao, Z Chen. The synergistic catalysis on Co nanoparticles and CoNx sites of aniline-modified ZIF derived Co@NCs for oxidative esterification of HMF. Chinese Chemical Letters, 2021, 32( 2): 685– 690 https://doi.org/10.1016/j.cclet.2020.06.027
44
Z Ma, T Song, Y Yuan, Y Yang. Synergistic catalysis on Fe–Nx sites and Fe nanoparticles for efficient synthesis of quinolines and quinazolinones via oxidative coupling of amines and aldehydes. Chemical Science (Cambridge), 2019, 10( 44): 10283– 10289 https://doi.org/10.1039/C9SC04060A
45
C H Li, Y Z Li, X X Luo, Z Y Li, H Zhang, H Li, S Yang. Catalytic cascade acetylation–alkylation of biofuran to C17 diesel precursor enabled by a budget acid-switchable catalyst. Chinese Journal of Chemical Engineering, 2021, 34 : 171– 179 https://doi.org/10.1016/j.cjche.2020.09.037
46
J Liu, H Zhang, J Y Wang, G M Zhao, D Liu. Relationship between the structure and dehydrogenation of alcohols/ hydrogenation of nitroarenes and base catalysis performance of Co–N–C catalyst. Reaction Kinetics, Mechanisms and Catalysis, 2020, 129( 2): 865– 881 https://doi.org/10.1007/s11144-020-01737-4
