Mechanistic study of bismuth-catalyzed direct benzylation of 2,4-pentanediones: the case of BiCl3 and generalization

  • K. Harrath
  • S. Boughdiri
  • R. Linguerri
  • M. Hochlaf
Regular Article


At present, we investigate the mechanisms for bismuth-catalyzed direct benzylation of 2,4-pentanediones using various density functional theories and post-Hartree–Fock ab initio methods. First, we deeply consider the role of BiCl3, where six scenarios are proposed. All of them start with the formation of a weakly bound complex between the BiCl3 catalyst and the alcohol or the dione. The most favorable one corresponds to the direct access to the products via a unique transition state (SN2-type mechanism). We also examined the effects of various nonpolar and polar solvents, which are viewed to slightly affect the energy profiles for SN2 and internal nucleophilic substitution (SNi) types of mechanism, whereas strong perturbations are observed for SN1 mechanism. For instance, the later one becomes the most thermodynamically favorable in DMSO solvent. In addition, several classes of benzyl alcohols and catalysts (BiX3, where X = Cl, Br, I, NO3, and OTf) were considered within the framework of SN2 and SNi mechanisms. The reactivity of these alcohols increases going from primary to secondary to tertiary. These findings are in line with the present available experimental results. Finally, our computations suggest that Bi(NO3)3 could be an excellent catalyst for the title reaction.


DFT Ab initio calculations Alkylation reaction Bismuth salts catalysts Transition state Reaction mechanism 



This research was financially supported by the Tunisian Ministry of Higher Education and Research and by a Marie Curie International Research Staff Exchange Scheme Fellowship within the 7th European Community Framework Program under Grant No PIRSES-GA-2012-31754, the COST Action CM1405 MOLIM.

Supplementary material

214_2015_1758_MOESM1_ESM.docx (500 kb)
Supplementary material 1 (DOCX 500 kb)


  1. 1.
    Samajdar S, Becker FF, Banik BK (2001) Synth Commun 31:2691CrossRefGoogle Scholar
  2. 2.
    Tymonko SA, Nattier BA, Mohan RS (1999) Tetrahedron Lett 40:7657CrossRefGoogle Scholar
  3. 3.
    Coin C, Zevaco T, Dunach E, Postel M (1996) Bull Soc Chim Fr 133:913Google Scholar
  4. 4.
    Komatsu N, Taniguchi A, Uda M, Suzuki H (1996) Chem Commun 1847Google Scholar
  5. 5.
    Sabitha G, Babu RS, Reddy EV, Yadav JS (2000) Chem Lett 9:1074CrossRefGoogle Scholar
  6. 6.
    Cong X, Hu F, Liu K-G, Liao Q-J, Yao Z-J (2005) J Org Chem 70:4514CrossRefGoogle Scholar
  7. 7.
    Bajwa JS, Vivelo J, Slade J, Repic O, Blacklock T (2000) Tetrahedron Lett 41:6021CrossRefGoogle Scholar
  8. 8.
    Boruah A, Baruah B, Prajapati D, Sandhu JS (1997) Synlett 11:1251CrossRefGoogle Scholar
  9. 9.
    Laurent-Robert H, Garrigues B, Dubac J (2001) Synlett 1160, Err 564 (2001)Google Scholar
  10. 10.
    Subba Reddy BV, Srinivas R, Yadav JS, Ramalingam T (2001) Synth Commun. 31:1075CrossRefGoogle Scholar
  11. 11.
    Komatsu N, Ishida J, Suzuki H (1997) Tetrahedron Lett 38:7219CrossRefGoogle Scholar
  12. 12.
    Ramalinga K, Vijayalakshmi P, Kaimal TNB (2001) Synlett 6:863CrossRefGoogle Scholar
  13. 13.
    Monk KA, Sarapa D, Mohan RS (2000) Synth Commun 30:3167CrossRefGoogle Scholar
  14. 14.
    Keramane E, Boyer B, Roque J-P (2001) Tetrahedron 57:1909CrossRefGoogle Scholar
  15. 15.
    Repichet S, Le Roux C, Dubac J, Desmurs JR (1998) Eur J Org Chem 1998:2743CrossRefGoogle Scholar
  16. 16.
    Le Roux C, Dubac J (2002) Synlett 2:181CrossRefGoogle Scholar
  17. 17.
    Rueping M, Nachtsheim BJ, Kuenkel A (2007) Org Lett 9:825CrossRefGoogle Scholar
  18. 18.
    Godeau J, Fontaine-Vive F, Antoniotti S, Duñach E (2012) Chem Eur J 18:16815CrossRefGoogle Scholar
  19. 19.
    Rueping M, Nachtsheim BJ, Ieawsuwan W (2006) Adv Synth Catal 348:1033CrossRefGoogle Scholar
  20. 20.
    Leonard NM, Wieland LC, Mohan RS (2002) Tetrahedron 58:8373CrossRefGoogle Scholar
  21. 21.
    Hua RM (2008) Curr Org Synth 5:1CrossRefGoogle Scholar
  22. 22.
    Ollevier T (ed) (2012) Bismuth-mediated organic reactions. Topics in current chemistry, Springer, HeidelbergGoogle Scholar
  23. 23.
    Ollevier T (2013) Org Biomol Chem 11:2740CrossRefGoogle Scholar
  24. 24.
    Yasuda M, Somyo T, Baba A (2006) Angew Chem Int Ed 45:793CrossRefGoogle Scholar
  25. 25.
    Jana U, Biswas S, Maiti S (2007) Tetrahedron Lett 48:4065CrossRefGoogle Scholar
  26. 26.
    Bisaro F, Pretat G, Vitale M, Poli G (2002) Synlett 11:1823Google Scholar
  27. 27.
    Masahiro N, Yosuke K, Keitaro I (2007) J Org Chem 72:5161CrossRefGoogle Scholar
  28. 28.
    Sanderson J, Bayse CA (2008) Tetrahedron 64:7685CrossRefGoogle Scholar
  29. 29.
    Barone V, Cossi M (1998) J Phys Chem A 102:1995CrossRefGoogle Scholar
  30. 30.
    Cossi M, Rega N, Scalmani G, Barone V (2003) J Comp Chem 24:669CrossRefGoogle Scholar
  31. 31.
    Gaussian 09, Revision D.01, Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JJA, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA, Gaussian, Inc., Wallingford CT, 2013Google Scholar
  32. 32.
    Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785CrossRefGoogle Scholar
  33. 33.
    Becke AD (1993) J Chem Phys 98:5648CrossRefGoogle Scholar
  34. 34.
    Adamo C, Barone V (1998) J Chem Phys 108:664CrossRefGoogle Scholar
  35. 35.
    Yanai T, Tew D, Handy N (2004) Chem Phys Lett 393:51CrossRefGoogle Scholar
  36. 36.
    Møller C, Plesset MS (1934) Phys Rev 46:618CrossRefGoogle Scholar
  37. 37.
    Raghavachari K, Trucks GW, Pople JA, Head-Gordon M (1989) Chem Phys Lett 157:479CrossRefGoogle Scholar
  38. 38.
    Purvis GD III, Bartlett RJ (1982) J Chem Phys 76:1910CrossRefGoogle Scholar
  39. 39.
    Dunning TH Jr, Hay PJ (1977) In: Schaefer III HF (ed) Modern theoretical chemistry. Plenum: New York, 1977, vol 3, pp 1–28Google Scholar
  40. 40.
    Wadt WR, Hay PJ (1985) J Chem Phys 82:284CrossRefGoogle Scholar
  41. 41.
    Dunning TH Jr (1989) J Chem Phys 90:1007CrossRefGoogle Scholar
  42. 42.
    Woon DE, Dunning TH Jr (1993) J. Chem. Phys. 98:1358CrossRefGoogle Scholar
  43. 43.
    Peterson KA (2003) J Chem Phys 119:11099CrossRefGoogle Scholar
  44. 44.
    Dunning TH Jr, Hay PJ (1977) In: Schaefer III HF Methods of electronic structure theory, Plenum Press, vol. 2Google Scholar
  45. 45.
    Hay PJ, Wadt WR (1985) J Chem Phys 82:270CrossRefGoogle Scholar
  46. 46.
    Hay PJ, Wadt WR (1985) J. Chem. Phys. 82:299CrossRefGoogle Scholar
  47. 47.
    Weinhold F, Carpenter JE (1988) In: Naaman R, Vager Z (eds) The structure of small molecules and ions. Plenum, 1988, pp. 227–236Google Scholar
  48. 48.
    Reed AE, Curtiss LA, Weinhold F (1988) Chem Rev 88:899CrossRefGoogle Scholar
  49. 49.
    Carpenter JE, Weinhold F (1988) J Mol Struct (Theochem) 46:41CrossRefGoogle Scholar
  50. 50.
    Chattaraj PK, Parr RG (1993) In: Sen KD, Mingos DMP (eds) Chemical hardness, structure and bonding. Springer: Berlin, vol. 80, pp. 11–25Google Scholar
  51. 51.
    Boussouf K, Boulmene R, Prakash M, Komiha N, Taleb M, Mogren Al-Mogren M, Hochlaf M (2015) Phys Chem Chem Phys 17:14417CrossRefGoogle Scholar
  52. 52.
    Marcus Y (1999) The properties of solvents, vol. 4, Wiley, England,‎ p 239. ISBN 978-0-471-98369-9, LCCN 98018212Google Scholar
  53. 53.
    Breidung J, Theil WJ (1992) Comput Chem 13:165CrossRefGoogle Scholar
  54. 54.
    Schwerdtfeger P, Hunt P (1999) Adv Mol Str 5:223CrossRefGoogle Scholar
  55. 55.
    Schultz G, Kolonits M, Hargittai M (1999) Struct Chem 10:321CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  1. 1.Unité de Recherche Physico-Chimie des Matériaux à l’Etat Condensé, Département de Chimie, Faculté des Sciences de TunisUniversité Tunis El ManarTunisTunisia
  2. 2.Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRSUniversité Paris-EstMarne-la-ValléeFrance

Personalised recommendations