Catalysis Letters

, Volume 149, Issue 1, pp 347–359 | Cite as

Cu@U-g-C3N4 Catalyzed Cyclization of o-Phenylenediamines for the Synthesis of Benzimidazoles by Using CO2 and Dimethylamine Borane as a Hydrogen Source

  • Vishal V. Phatake
  • Bhalchandra M. BhanageEmail author


This work reports a green and sustainable route for the synthesis of benzimidazoles via C–N bond formation using carbon dioxide (CO2) as a C1 carbon source. In this work, Cu@U-g-C3N4 catalyst was prepared from urea derived porous graphitic carbon nitride (U-g-C3N4) and CuCl2 and characterized by FT-IR, XRD, XPS, SEM, TPD etc. The Cu@U-g-C3N4 as a heterogeneous recyclable catalyst has been employed first time for the cyclization of o-phenylenediamines (OPD) with CO2 to benzimidazoles using dimethylamine borane (DMAB). The proposed protocol becomes sustainable and efficient due to the use of propylene carbonate/water as a suitable biodegradable, economical and environmentally benign solvent system. The proposed catalytic system showed a wide range of substrate scope for the synthesis of benzimidazoles in good to excellent yields.

Graphical Abstract


Cu@U-g-C3N4 Heterogeneous catalyst Carbon dioxide fixation DMAB Amines Green solvent Benzimidazoles 



The author Vishal V. Phatake would like to thanks University Grant Commission (UGC), New Delhi, India for providing a Junior Research Fellowship under UGC-NET JRF scheme.

Compliance with Ethical Standards

Conflict of interest

No conflict of interest, for each contributing author.

Supplementary material

10562_2018_2608_MOESM1_ESM.doc (2.3 mb)
Supplementary material 1 (DOC 2397 KB)


  1. 1.
    Bhanage BM, Arai M (2014) Transformation and utilization of carbon dioxide. Springer, Berlin, HeidelbergCrossRefGoogle Scholar
  2. 2.
    He M, Sun Y, Han B (2013) Angew Chemie Int Ed 52:9620–9633CrossRefGoogle Scholar
  3. 3.
    Liu Q, Wu L, Jackstell R, Beller M (2015) Nat Commun 6:5933CrossRefGoogle Scholar
  4. 4.
    Aresta M (2006) Carbon dioxide reduction and uses as a chemical feedstock. In: Activation of small molecules. Wiley, Weinheim, pp 1–41Google Scholar
  5. 5.
    Nale D, Bhanage B (2016) Synlett 27:1413–1417CrossRefGoogle Scholar
  6. 6.
    Saptal VB, Sasaki T, Harada K, Nishio-Hamane D, Bhanage BM (2016) ChemSusChem 9:644–650CrossRefGoogle Scholar
  7. 7.
    Saptal VB, Bhanage BM (2016) ChemCatChem 8:244–250CrossRefGoogle Scholar
  8. 8.
    Nale DB, Rana S, Parida K, Bhanage BM (2014) Appl Catal A Gen 469:340–349CrossRefGoogle Scholar
  9. 9.
    Fontana F, Chen CC, Aggarwal VK (2011) Org Lett 13:3454–3457CrossRefGoogle Scholar
  10. 10.
    Jiang T, Ma X, Zhou Y, Liang S, Zhang J, Han B (2008) Green Chem 10:465CrossRefGoogle Scholar
  11. 11.
    Wesselbaum S, vom Stein T, Klankermayer J, Leitner W (2012) Angew Chemie Int Ed 51:7499–7502CrossRefGoogle Scholar
  12. 12.
    Moret S, Dyson PJ, Laurenczy G (2014) Nat Commun 5:4017CrossRefGoogle Scholar
  13. 13.
    Saptal VB, Bhanage BM (2017) ChemSusChem 10:1145–1151CrossRefGoogle Scholar
  14. 14.
    Nale DB, Saigaonkar SD, Bhanage BM (2014) J CO2 Util 8:67–73CrossRefGoogle Scholar
  15. 15.
    Wang W-H, Feng X, Bao M (2018) Transformation of carbon dioxide to formic acid and methanol. Springer SingaporeGoogle Scholar
  16. 16.
    Li Y, Cui X, Dong K et al (2017) ACS Catal 7:1077–1086CrossRefGoogle Scholar
  17. 17.
    Vojčić N, Bregović N, Cindro N et al (2017) ChemistrySelect 2:4899–4905CrossRefGoogle Scholar
  18. 18.
    Keri RS, Hiremathad A, Budagumpi S, Nagaraja BM (2015) Chem Biol Drug Des 86:19–65CrossRefGoogle Scholar
  19. 19.
    Zhang J, Wang J-L, Zhou Z-M et al (2012) Bioorg Med Chem 20:4208–4216CrossRefGoogle Scholar
  20. 20.
    Zhou R, Skibo EB (1996) J Med Chem 39:4321–4331CrossRefGoogle Scholar
  21. 21.
    Azizi N, Edrisi M, Abbasi F (2018) Appl Organomet Chem 32:e3901CrossRefGoogle Scholar
  22. 22.
    Nale D, Bhanage B (2015) Synlett 26:2835–2842CrossRefGoogle Scholar
  23. 23.
    Kattimani PP, Kamble RR, Meti GY (2015) RSC Adv 5:29447–29455CrossRefGoogle Scholar
  24. 24.
    Fu R, Yang Y, Ma Y et al (2015) Tetrahedron Lett 56:4527–4531CrossRefGoogle Scholar
  25. 25.
    Mann J, Baron A, Opoku-Boahen Y et al (2001) J Med Chem 44:138–144CrossRefGoogle Scholar
  26. 26.
    Lin S, Yang L (2005) Tetrahedron Lett 46:4315–4319CrossRefGoogle Scholar
  27. 27.
    Aksenov AV, Smirnov AN, Aksenov NA et al (2015) Org Biomol Chem 13:4289–4295CrossRefGoogle Scholar
  28. 28.
    Feng F, Ye J, Cheng Z et al (2016) RSC Adv 6:72750–72755CrossRefGoogle Scholar
  29. 29.
    Yu B, Zhang H, Zhao Y et al (2013) Green Chem 15:95–99CrossRefGoogle Scholar
  30. 30.
    Hao L, Zhao Y, Yu B et al (2014) Green Chem 16:3039CrossRefGoogle Scholar
  31. 31.
    Jacquet O, Das Neves Gomes C, Ephritikhine M, Cantat T (2013) ChemCatChem 5:117–120CrossRefGoogle Scholar
  32. 32.
    Zhang Z, Sun Q, Xia C, Sun W (2016) Org Lett 18:6316–6319CrossRefGoogle Scholar
  33. 33.
    Shaikh A-AG, Sivaram S (1996) Organic carbonates. Chem Rev 96:951–976CrossRefGoogle Scholar
  34. 34.
    Adeleye AI, Patel D, Niyogi D, Saha B (2014) Ind Eng Chem Res 53:18647–18657CrossRefGoogle Scholar
  35. 35.
    Alder CM, Hayler JD, Henderson RK et al (2016) Green Chem 18:3879–3890CrossRefGoogle Scholar
  36. 36.
    Gautam P, Kathe P, Bhanage BM (2017) Green Chem 19:823–830CrossRefGoogle Scholar
  37. 37.
    Parker HL, Sherwood J, Hunt AJ, Clark JH (2014) ACS Sustain Chem Eng 2:1739–1742CrossRefGoogle Scholar
  38. 38.
    Dong G, Zhang Y, Pan Q, Qiu J (2014) J Photochem Photobiol C Photochem Rev 20:33–50CrossRefGoogle Scholar
  39. 39.
    Gillan EG (2000) Chem Mater 12:3906–3912CrossRefGoogle Scholar
  40. 40.
    Wang Y, Wang X, Antonietti M (2012) Angew Chemie Int Ed 51:68–89CrossRefGoogle Scholar
  41. 41.
    Fang H-B, Luo Y, Zheng Y-Z, Ma W, Tao X (2016) Ind Eng Chem Res 55:4506–4514CrossRefGoogle Scholar
  42. 42.
    Huang S, Zhao Y, Tang R (2016) RSC Adv 6:90887–90896CrossRefGoogle Scholar
  43. 43.
    Zhang S, Mei Q, Liu H et al (2016) RSC Adv 6:32370–32373CrossRefGoogle Scholar
  44. 44.
    Saptal VB, Juneja G, Bhanage BM (2018) New J ChemGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of ChemistryInstitute of Chemical Technology (ICT)MumbaiIndia

Personalised recommendations