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Investigation of the solvent effect, regioselectivity, and the mechanism of the cycloaddition reaction between 2-chlorobenzimidazole and benzonitrile oxide

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Chemistry of Heterocyclic Compounds Aims and scope

This theoretical study, performed using density functional theory at the B3LYP/6-311+G(d,p) level, shows that the most likely route to obtain 3-phenyl[1,2,4]oxadiazolo[4,5-a]benzimidazole from the reaction of 2-chlorobenzimidazole with benzonitrile oxide implies the presence of anionic species. A concerted [3+2] cycloaddition reaction on the imidoyl group of 2-chlorobenzimidazole is not possible. The presence of a polar protic solvent (MeOH) favors the reaction. The analysis of the Wiberg indices shows that the transition states are earlier in MeOH than in THF or gas phase. Finally, topological analysis of the electron localization function indicates that the formation of the N4–C3 and C5–O bonds and the breaking of the C5–Cl bond in the preparation of 3-phenyl[1,2,4]oxadiazolo[4,5-a]benzimidazole are marked for each by the presence of an asynaptic basin V(Asyn) and proceed through tetrahedral intermediates, indicating the nonconcerted nature of the mechanism. These results are in good agreement with the experimental results.

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References

  1. Çevik, U. A.; Osmaniye, D.; Çavuşoğlu, B. K.; Sağlik, B. N.; Levent, S.; Ilgin, S.; Can, N. Ö.; Özkay, Y.; Kaplancıklı, Z. A. Med. Chem. Res. 2019, 28, 2252.

    Article  Google Scholar 

  2. Gupta, V. K.; Kaur, B.; Kaur, A.; Kaur, A.; Gupta, M. Ind. J. Pharm. Biol. Res. 2018, 6(2), 64.

    Article  CAS  Google Scholar 

  3. Rashid, M.; Husain, A.; Mishra, R. Eur. J. Med. Chem. 2012, 54, 855.

    Article  CAS  PubMed  Google Scholar 

  4. Acar Çevik, U.; Sağlık, B. N.; Osmaniye, D.; Levent, S.; Kaya Çavuşoğlu, B.; Karaduman, A. B.; Eklioğlu, Ö. A.; Özkay, Y.; Kaplancıklı, Z. A. J. Enzyme Inhib. Med. Chem. 2020, 35, 1657.

    Article  PubMed  PubMed Central  Google Scholar 

  5. Rathore, A.; Rahman, M. U.; Siddiqui, A. A.; Ali, A.; Shaharyar, M. Arch. Pharm. 2014, 347, 923.

    Article  CAS  Google Scholar 

  6. Kamal, A.; Reddy, T. S.; Vishnuvardhan, M. V. P. S.; Nimbarte, V. D.; Subba Rao, A. V.; Srinivasulu, V.; Shankaraiah, N. Bioorg. Med. Chem. 2015, 23, 4608.

    Article  CAS  PubMed  Google Scholar 

  7. Palumbo Piccionello, A. Int. J. Mol. Sci. 2021, 22, 3988.

    Article  PubMed  PubMed Central  Google Scholar 

  8. Jiang, K.-M.; Zhang, J.-Q.; Jin, Y.; Lin, J. Asian J. Org. Chem. 2017, 6, 1620.

    CAS  Google Scholar 

  9. Jawalekar, A. M.; Reubsaet, E.; Rutjes, F. P. J. T.; van Delft, F. L. Chem. Commun. 2011, 47, 3198.

    Article  CAS  Google Scholar 

  10. Zhao, G.; Liang, L.; Wen, C. H. E.; Tong, R. Org. Lett. 2019, 21, 315.

    Article  CAS  PubMed  Google Scholar 

  11. Lin, B.; Yu, P.; He, C. Q.; Houk, K. N. Bioorg. Med. Chem. 2016, 24, 4787.

    Article  PubMed  Google Scholar 

  12. Ouahdi, Z.; Ourhriss, N.; Oualed Aitouna, A.; Barhoumi, A.; Belghiti, M. E.; Moubarik, A.; El Abdallaoui, H. E. A.; El Idrissi, M.; Zeroual, A. Theor. Chem. Acc. 2022, 141, 50.

    Article  CAS  Google Scholar 

  13. Zeroual, A.; Ríos-Gutiérrez, M.; El Idrissi, M.; El Abdallaoui, H. E. A.; Domingo, L. R. Int. J. Quantum Chem. 2019, 119, e25980.

    Article  Google Scholar 

  14. Domingo, L. R.; Chamorro, E.; Pérez, P. Eur. J. Org. Chem. 2009, 3036.

  15. El Idrissi, M.; El Ghozlani, M.; Eşme, A.; Ríos-Gutiérrez, M.; Ouled Aitouna, A.; Salah, M.; El Abdallaoui, H. E. A.; Zeroual, A.; Mazoir, N. Organics 2021, 2, 1.

    Article  Google Scholar 

  16. Zahnoune, R.; Asserne, F.; Ourhriss, N.; Ouled Aitouna, A.; Barhoumi, A.; Hakmaoui Y.; Belghiti, M. E.; Abouricha, S.; El ajlaoui, R.; Zeroual, A. J. Mol. Struct. 2022, 1269, 133630.

  17. Domingo, L. R.; Aurell, M. J.; Pérez, P. Tetrahedron 2014, 70, 4519.

    Article  CAS  Google Scholar 

  18. Domingo, L. R.; Emamian, S. R. Tetrahedron 2014, 70, 1267.

    Article  CAS  Google Scholar 

  19. Ríos-Gutiérez, M.; Domingo, L. R. Eur. J. Org. Chem. 2018, 267.

  20. Domingo, L. R.; Sáez, J. A. Org. Biomol. Chem. 2009, 7, 3576.

    Article  CAS  PubMed  Google Scholar 

  21. Domingo, L. R.; Aurell, M. J.; Jalal, R.; Esseffar, M. J. Mol. Struct.: THEOCHEM 2010, 942, 26.

    Article  CAS  Google Scholar 

  22. Mohammad-Salim, H. A.; Ahmed Basheer, H.; Abdallah, H. H.; Zeroual, A.; Abdi Jamil, L. New J. Chem. 2021, 45, 262.

    Article  CAS  Google Scholar 

  23. Salah, M.; Belghiti, M. E.; Aitouna, A. O.; Zeroual, A.; Jorio, S.; El Alaoui Abdellaoui, H.; El Hadki, H.; Marakchi, K.; Komiha, N. J. Mol. Graphics Modell. 2021, 102, 107763.

    Article  CAS  Google Scholar 

  24. Harrison, D.; Ralph, J. T. J. Chem. Soc. 1965, 236.

  25. Lunn, W. H. W.; Harper, R. W. J. Heterocycl. Chem. 1971, 8, 141.

    Article  CAS  Google Scholar 

  26. Ponomar', V. S.; Kochergin, P. M. Chem. Heterocycl. Compd. 1972, 8, 229.

    Article  Google Scholar 

  27. Ajay, A.; Gupt, M. P.; Devender, N.; Tripathi, R. P. Mol. Diversity 2012, 16, 335.

    Article  CAS  Google Scholar 

  28. Tanaka, M.; Ubukata, M.; Matsuo, T.; Yasue, K.; Matsumoto, K.; Kajimoto, Y.; Ogo T.; Inaba, T. Org. Lett. 2007, 9, 3331.

    Article  CAS  PubMed  Google Scholar 

  29. Scrocco, E.; Tomasi, J. Adv. Quantum Chem. 1978, 11, 115.

    Article  CAS  Google Scholar 

  30. Zeroual, A.; Ríos-Gutiérrez, M.; El Ghozlani, M.; El Idrissi, M.; Ouled Aitouna, A.; Salah, M.; El Alaoui, El Abdallaoui, H.; Domingo, L. R. Theor. Chem. Acc. 2020, 139, 37.

  31. Fukui, K. Acc. Chem. Res. 1981, 14, 363.

    Article  CAS  Google Scholar 

  32. Sun, P.; Liu, M.; Pu, W.; Jin, Y.; Liu, S.; Cao, Q.; Ding, Z. Authorea 2020. DOI: https://doi.org/10.22541/au.159078914.44654675.

    Article  Google Scholar 

  33. Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735.

    Article  CAS  Google Scholar 

  34. Fukui, K. J. Phys. Chem. 1970, 74, 4161.

    Article  CAS  Google Scholar 

  35. Wiberg, K. B. Tetrahedron 1968, 24, 1083.

    Article  CAS  Google Scholar 

  36. Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899.

    Article  CAS  Google Scholar 

  37. Glendening, E. D.; Landis, C. R.; Weinhold, F. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2012, 2, 1.

  38. Becke, A. D.; Edgecombe, K. E. J. Chem Phys. 1990, 92, 5397.

    CAS  Google Scholar 

  39. Cossi, M.; Rega, N.; Scalmani, G.; Barone, V. J. Comput. Chem. 2003, 24(6), 669.

    Article  CAS  PubMed  Google Scholar 

  40. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A.; Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision E.01; Gaussian, Inc.: Wallingford, 2009.

  41. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B: Condens. Matter Mater. Phys. 1988, 37, 785.

    Article  CAS  Google Scholar 

  42. Becke, A. D. J. Chem. Phys. 1993, 98, 5648.

    Article  CAS  Google Scholar 

  43. Parr, R. G.; Szentpály, L. v.; Liu, S. J. Am. Chem. Soc. 1999, 121, 1922.

  44. Domingo, L. R.; Chamorro, E.; Pérez, P. J. Org. Chem. 2008, 73, 4615.

    Article  CAS  PubMed  Google Scholar 

  45. Domingo, L. R.; Pérez, P. Org. Biomol. Chem. 2011, 9, 7168.

    Article  CAS  PubMed  Google Scholar 

  46. Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, A1133.

    Article  Google Scholar 

  47. Domingo, L. R.; Pérez, P.; Sáez, J. A. RSC Adv. 2013, 3, 1486.

    Article  CAS  Google Scholar 

  48. Domingo, L. R. RSC Adv. 2014, 4, 32415.

    Article  CAS  Google Scholar 

  49. Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899.

    Article  CAS  Google Scholar 

  50. Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735.

    Article  CAS  Google Scholar 

  51. Zeroual, A.; Ríos-Gutiérrez, M.; Salah, M.; El Alaoui El Abdallaoui, H.; Domingo, L. R. J. Chem. Sci. (Berlin, Ger.) 2019, 131, 75.

  52. El Ghozlani, M.; Barhoumi, A.; Elkacmi, R.; Ouled Aitouna, A.; Zeroual, A.; El Idrissi, M. Chem. Afr. 2020, 3, 901.

    Article  Google Scholar 

  53. Tamilmani, V.; Daul, C. A.; Lage Robles, J.; Bochet, C. G.; Venuvanalingam, P. Chem. Phys. Lett. 2005, 406, 355.

    Article  CAS  Google Scholar 

  54. Noury, S.; Krokidis, X.; Fuster, F.; Silvi, B. Comput. Chem. (Oxford, U. K.) 1999, 23, 597.

  55. Ouled Aitouna, Ab.; Barhoumi, A.; El Idrissi, M.; Ouled Aitouna, A.; Zeroual, A.; Mazoir, N.; Chakroun, A.; Benharref, A. Mor. J. Chem. 2021. DOI: https://doi.org/10.48317/IMIST.PRSM/morjchem-v9i1.20462.

  56. Wiberg, K. B.; Rablen, P. R. J. Comput. Chem. 1993, 14, 1504.

    Article  CAS  Google Scholar 

  57. Divya, P.; Bena Jothy, V. Chem. Phys. Lett. 2018, 695, 1.

    Article  CAS  Google Scholar 

  58. Merino, P.; Chiacchio, M.; Legnani, L.; Tejero, T. Molecules 2017, 22, 1371.

    Article  PubMed  PubMed Central  Google Scholar 

  59. Abbiche, K.; Mohammad-Salim, H.; Salah, M.; Mazoir, N.; Zeroual, A.; El Alaoui El Abdallaoui, H.; El Hammadi, A.; Hilali, M.; Abdallah, H. H.; Hochlaf, M. Theor. Chem. Acc. 2020, 139, 148.

  60. Ouled Aitouna, A.; Belghiti, M. E.; Eşme, A.; Ouled Aitouna, A.; Salah, M.; Chekroun, A.; El Alaoui El Abdallaoui, H.; Benharref, A.; Mazoir, N.; Zeroual, A.; Nejjari, C. J. Mol. Struct. 2021, 1244, 130864.

  61. Zawadzińska, K.; Ríos-Gutiérrez, M.; Kula, K.; Woliński, P.; Mirosław, B.; Krawczyk, T.; Jasiński, R. Molecules 2021, 26, 6774.

    Article  PubMed  PubMed Central  Google Scholar 

  62. Jasiński, R.; Jasińska, E.; Dresler, E. J. Mol. Model. 2017, 23, 13.

    Article  PubMed  Google Scholar 

  63. Zawadzińska, K.; Kula, K. Organics 2021, 2, 26.

    Article  Google Scholar 

  64. Du, P.; Zhao, J.; Liu, S.; Yue, Z. RSC Adv. 2021, 11, 24238.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  65. Li, H. G.; Kim, C. K.; Lee, B.-S.; Kim, C. K.; Rhee, S. K.; Lee, I. J. Am. Chem. Soc. 2001, 123, 2326.

    Article  CAS  PubMed  Google Scholar 

  66. Zeroual, A.; El Hajbi, A. Can. Chem. Trans. 2015, 3, 430.

    CAS  Google Scholar 

  67. Salah, M.; Zeroual, A.; Jorio, S.; El Hadki, H.; Kabbaj, O.; Marakchi, K.; Komiha, N. J. Mol. Graphics Modell. 2020, 94, 107458.

    Article  CAS  Google Scholar 

  68. Melin, J.; Seabra, G.; Ortiz, J. V. In Theoretical Aspects of Chemical Reactivity; Toro-Labbé, A., Ed.; Elsevier: Amsterdam, 2007, p. 87.

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Authors and Affiliations

  1. Molecular Modelling, Spectroscopy and Environment Research Team, Faculty of Science, Chouaïb Doukkali University, P. O. Box 20, 24000, El Jadida, Morocco

    Mohamed Abdoul-Hakim, Khadija El Idrissi & Abdellah Zeroual

  2. Analytical Chemistry and Environmental Sciences Team, Department of chemistry, Faculty of Science, Chouaib Doukkali University, P. O. Box 20, 24000, El Jadida, Morocco

    Mohamed Abdoul-Hakim, Khadija El Idrissi & Hocine Garmes

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  1. Mohamed Abdoul-Hakim
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  2. Khadija El Idrissi
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Correspondence to Abdellah Zeroual.

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Published in Khimiya Geterotsiklicheskikh Soedinenii, 2023, 59(3), 155–164

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Abdoul-Hakim, M., Idrissi, K.E., Zeroual, A. et al. Investigation of the solvent effect, regioselectivity, and the mechanism of the cycloaddition reaction between 2-chlorobenzimidazole and benzonitrile oxide. Chem Heterocycl Comp 59, 155–164 (2023). https://doi.org/10.1007/s10593-023-03177-z

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