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A conceptual DFT approach towards analysing feasibility of the intramolecular cycloaddition Diels-Alder reaction of triene amide in Lewis acid catalyst

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Abstract

The effect of Lewis acid catalysts, TiCl4 and Et2AlCl on the intramolecular cycloaddition Diels-Alder (IMDA) reaction of triene-amide have been studied theoretically using the DFT (Density Functional Theory) at the 6-31G(d,p) level of theory. The results obtained using the polar model of Domingo, electrophilicity, nucleophilicity indices and thermochemistry computations, demonstrate that these catalysts are coordinated with more nucleophilic atoms of diene fragment (nitrogen and oxygen of amide group). These catalysts affect negatively the feasibility of the reaction as well as the physico-chemical parameters of the IMDA reaction of triene-amide.

Lewis acids have negative effects on the intramolecular Diels-Alder (IMDA) reaction of triene amide, neither acceleration nor better selectivity. In addition, the IMDA reaction is delayed or unfeasible when Lewis acids is coordinated to the more nucleophilic atoms of O11 and N9 in diene fragment.

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References

  1. Yates P and Eaton P 1960 J. Am. Chem. Soc. 82 4436

    Article  CAS  Google Scholar 

  2. Kagan H B and Riant O 1992 Chem. Rev. 92 1007

    Article  CAS  Google Scholar 

  3. Pindur U, Lutz G and Otto C 1993 Chem. Rev. 93 741

    Article  CAS  Google Scholar 

  4. Birney D M and Houk K N 1990 J. Am. Chem. Soc. 112 4127

    Article  CAS  Google Scholar 

  5. Yamabe S, Dai T and Minato T 1995 J. Am. Chem. Soc. 117 10994

    Article  CAS  Google Scholar 

  6. Sbai A, Branchadell V, Ortuño R M and Oliva A 1997 J. Org. Chem. 62 3049

    Article  CAS  Google Scholar 

  7. Garcia J I, Martinez-Merino V, Mayoral J A and Salvatella L 1998 J. Am. Chem. Soc. 120 2415

    Article  CAS  Google Scholar 

  8. Yambe S and Minato T 2000 J. Org. Chem. 65 1830

    Article  Google Scholar 

  9. Alves C N, Carneiro A S, Andrés J and Domingo L R 2006 Tetrahedron 62 5502

    Article  CAS  Google Scholar 

  10. Xia Y, Yin D, Rong C, Xu Q and Liu S 2008 J. Phys. Chem. A. 112 9970

    Article  CAS  Google Scholar 

  11. Geerlings P, Proft F D and Langenaeker W 2003 Chem. Rev. 103 1793

    Article  CAS  Google Scholar 

  12. Chattaraj P K, Sarkar U and Roy D R 2006 Chem. Rev. 106 2065

    Article  CAS  Google Scholar 

  13. Domingo L R, Asensio A and Arroyo P 2002 J. Phys. Org. Chem. 15 660

    Article  CAS  Google Scholar 

  14. Domingo L R and Sáez J A 2009 J. Org. Biomol. Chem. 7 3576

    Article  CAS  Google Scholar 

  15. Ess D H, Jones G O and Houk K N 2006 Adv. Synth. Catal. 348 2337

    Article  CAS  Google Scholar 

  16. Garmes H 1995 In Triene-amides synthesis from homoallylic azides, Diels-Alder cycloaddition Thesis (El Jadida: Chouaib Doukkali University)

  17. Benallou A, Garmes H and El Alaoui El Abdallaoui H 2014 Mor. J. Chem. 2 181

    Google Scholar 

  18. Benallou A, Garmes H and El Alaoui El Abdallaoui H 2016 Tetrahedron 72 76

    Article  CAS  Google Scholar 

  19. Benallou A, Garmes H and El Alaoui El Abdallaoui H 2014 IJIAS 8 685

    Google Scholar 

  20. Becke A D 1993 J. Chem. Phys. 98 5648

    Article  CAS  Google Scholar 

  21. Hehre W J, Radom L, Schleyer P von R and Pople J A (Eds.) 1986 In Ab Initio Molecular Orbital Theory (New York: Wiley)

  22. Schlegel H B 1982 J. Comput. Chem. 3 214

    Article  CAS  Google Scholar 

  23. 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, 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 O, Foresman J B, Ortiz J V, Cioslowski J and Fox D J 2009 In Gaussian, Revision A.02 (Wallingford CT : Gaussian Inc.)

    Google Scholar 

  24. Parr R G, Szentpaly L V and Liu S 1999 J. Am. Chem. Soc. 121 1922

    Article  CAS  Google Scholar 

  25. Parr R G and Pearson R G 1983 J. Am. Chem. Soc. 105 7512

    Article  CAS  Google Scholar 

  26. Domingo L R and Pérez P 2011 Org. Biomol. Chem. 9 7168

    Article  CAS  Google Scholar 

  27. Kohn W and Sham L J 1965 Phys. Rev. 140 1133

    Article  Google Scholar 

  28. Domingo L R and Săez J A 2009 Org. Biomol. Chem. 7 3576

    Article  CAS  Google Scholar 

  29. Yang W and Mortier W J 1986 J. Am. Chem. Soc. 108 5708

    Article  CAS  Google Scholar 

  30. Soto-Delgado J, Domingo L R and Contreras R 2010 Org. Biomol. Chem. 8 3678

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  32. Snider B B and Ron E 1985 J. Am. Chem. Soc. 107 8160

    Article  CAS  Google Scholar 

  33. Singleton D A and Hang C 2000 J. Org. Chem. 65 895

    Article  CAS  Google Scholar 

  34. Loncharich R J and Houk K N 1987 J. Am. Chem. Soc. 109 6947

    Article  CAS  Google Scholar 

  35. Domingo L R, Chamorro E and Pérez P 2008 J. Org. Chem. 73 4615

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Chemoinformatics Research and Spectroscopy and Quantum chemistry, Physical Chemistry Laboratory, Faculty of Science El Jadida, Chouaib Doukkali University, B. P. 20, 2300, El Jadida, Morocco

    ABDELILAH BENALLOU & HABIB EL ALAOUI EL ABDALLAOUI

  2. Laboratory of Bio-organic chemistry, Department of Chemistry, Faculty of Science El Jadida, Chouaib Doukkali University, B. P. 20, 2300, El Jadida, Morocco

    HOCINE GARMES

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  1. ABDELILAH BENALLOU
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  2. HABIB EL ALAOUI EL ABDALLAOUI
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  3. HOCINE GARMES
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BENALLOU, A., ALAOUI EL ABDALLAOUI, H.E. & GARMES, H. A conceptual DFT approach towards analysing feasibility of the intramolecular cycloaddition Diels-Alder reaction of triene amide in Lewis acid catalyst. J Chem Sci 128, 1489–1496 (2016). https://doi.org/10.1007/s12039-016-1138-5

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  • DOI: https://doi.org/10.1007/s12039-016-1138-5

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