Journal of Chemical Sciences

, 121:859 | Cite as

Fluorine effect on pericyclic and pseudopericyclic processes: Evidences and ab initio theory

  • Lakshminarayanan Akilandeswari
  • Madhavan Jaccob
  • Ponnambalam Venuvanalingam
Article
First Online:

Abstract

Electrocyclic ring opening (ERO) reactions of 2-pyrone, 2-pyranol and pyran and their fluoro compounds (1–6) have been studied at MP2/6-31G(d) level with special emphasis on the influence of fluorine on these pericyclic/pseudopericyclic processes. Calculations clearly predict that substitution of fluorine at C6 favour the reaction both kinetically and thermodynamically. Magnetic susceptibility anisotropy (Δχ aniso), NICS(0), NBO and bond critical property (BCP) analyses clearly illustrate the following; 2-pyrone (1) and 6-fluoro-2-pyrone (2) reactions are pseudopericyclic; 6-fluoro-2-pyranol (reaction 4) corresponds to a borderline case; 2-pyranol (3) and pyran (5) and 6-fluoro pyran (6) reactions are clearly pericyclic in character. Correspondingly pseudeopericyclic reactions show up orbital disconnections and fluorine delays the occurrence of orbital disconnections on the reaction trajectory.

Keywords

Pericyclic reaction pseudeopericyclic reaction fluorine NICS(0) orbital disconnections NBO analysis 
This is a preview of subscription content, log in to check access.

References

  1. 1.
    Lemal D 1976 J. Am. Chem. Soc. 98 4325CrossRefGoogle Scholar
  2. 2.
    Birney D M and Wagenseller P E 1994 J. Am. Chem. Soc. 116 6262CrossRefGoogle Scholar
  3. 3.
    Birney D M, Ham S and Unruh G R 1997 J. Am. Chem. Soc. 119 4509CrossRefGoogle Scholar
  4. 4. (a)
    Birney D M, Xu X and Ham S 1999 Angew. Chem., Int. Ed. 38 189CrossRefGoogle Scholar
  5. 4. (b)
    Birney D M 2000 J. Am. Chem. Soc. 122 10917CrossRefGoogle Scholar
  6. 5.
    Shumway W W, Dalley N K and Birney D M 2001 J. Org. Chem. 66 5832CrossRefGoogle Scholar
  7. 6.
    Zhou C and Birney D M 2002 J. Am. Chem. Soc. 124 5237Google Scholar
  8. 7.
    Herges R, Jiao H and Schleyer P v R 1994 Angew. Chem., Int. Ed. Engl. 33 1376CrossRefGoogle Scholar
  9. 8.
    Schleyer P v R, Maerker C, Dransfeld A, Jiao H and van Eikema Hommes N J R 1996 J. Am. Chem. Soc. 118 6317CrossRefGoogle Scholar
  10. 9.
    Herges R and Geuenich D 2001 J. Phys. Chem A 105 3214CrossRefGoogle Scholar
  11. 10.
    Herges R and Papafilippopoulos A 2001 Angew. Chem., Int. Ed. Engl. 40 4671CrossRefGoogle Scholar
  12. 11.
    Kimball D B, Weakley T J R, Herges R and Haley M M 2002 J. Am. Chem. Soc. 124 13463CrossRefGoogle Scholar
  13. 12.
    Geuenich D, Hess K, Köhler F and Herges R 2005 Chem. Rev. 105 3758CrossRefGoogle Scholar
  14. 13.
    Rodríguez-Otero J and Cabaleiro-Lago E M 2002 Angew. Chem., Int. Ed. 41 1147CrossRefGoogle Scholar
  15. 14.
    Rodríguez-Otero J and Cabaleiro-Lago E M 2002 Chem. Eur. J. 2003 9 1837CrossRefGoogle Scholar
  16. 15.
    Cabaleiro-Lago E M, Rodríguez-Otero J and Hermida-Ramón J M 2003 J. Phys. Chem A 107 4962CrossRefGoogle Scholar
  17. 16.
    Rodríguez-Otero J, Cabaleiro-Lago E M, Hermida-Ramón J M and Peña-Gallego A 2003 J. Org. Chem. 68 8823CrossRefGoogle Scholar
  18. 17.
    Montero-Campillo M M, Rodríguez-Otero J and Cabaleiro-Lago E M 2004 J. Phys. Chem A 108 8373CrossRefGoogle Scholar
  19. 18.
    Cabaleiro-Lago E M, Rodríguez-Otero J, Varela-Varela S M, Peña-Gallego A and Hermida-Ramón J 2005 J. Org. Chem. 70 392CrossRefGoogle Scholar
  20. 19.
    Cabaleiro-Lago E M, Rodríguez-Otero J, González-López I, Peña-Gallego and Hermida-Ramón J 2005 J. Phys. Chem A 109 5636CrossRefGoogle Scholar
  21. 20.
    López C S, Faza O N, Cossío F P, Cork D M and de Lera A R 2005 Chem. Eur. J. 2005 11 1734CrossRefGoogle Scholar
  22. 21.
    Savin A, Nesper R, Wengert S and Fässler T F 1997 Angew. Chem., Int. Ed. Engl. 36 1808CrossRefGoogle Scholar
  23. 22.
    Chamorro E 2003 J. Chem. Phys. 118 8687CrossRefGoogle Scholar
  24. 23.
    Chamorro E and Notario R 2004 J. Phys. Chem A 108 4099CrossRefGoogle Scholar
  25. 24.
    Chamorro E and Notario R 2005 J. Phys. Chem A 109 7594; Chamorro E and Notario R 2005 J. Phys. Chem A 109 4352CrossRefGoogle Scholar
  26. 25.
    Maito E, Poater J, Duran M and Sola M 2006 Chem. Phys. Chem. 7 111–113Google Scholar
  27. 26.
    Calvo-Losada S and Quirante Sánchez J J 2008 J. Phys. Chem A 112 8164CrossRefGoogle Scholar
  28. 27.
    Birney D M 1996 J. Org. Chem. 61 243CrossRefGoogle Scholar
  29. 28.
    Rodríguez-Otero J and Cabaleiro-Lago E M 2003 Chem. Eur. J. 9 1837CrossRefGoogle Scholar
  30. 29.
    Akilandeswari L and Venuvanalingam P 2007 J. Theor. Comp. Chem. 6 233CrossRefGoogle Scholar
  31. 30.
    Akilandeswari L 2008 Ph D Thesis, Bharathidasan UniversityGoogle Scholar
  32. 31.
    Karney W L and Borden W T 1997 J. Am. Chem. Soc. 119 3347CrossRefGoogle Scholar
  33. 32.
    Borden W T 1998 Chem. Commun. 1919Google Scholar
  34. 33.
    Barone V and Adamo C 1996 J. Chem. Phys. 105 11007CrossRefGoogle Scholar
  35. 34.
    Reva I, Breda S, Roseiro T, Eusébio S and Fausto R 2005 J. Org. Chem. 70 7701CrossRefGoogle Scholar
  36. 35.
    Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Zakrzewski V G, Montgomery J, Stratmann R E, Burant J C, pprich, Millam J M, Daniels A D, Kudin K N, Strain M C, Farkas O, Tomasi J, Barone V, Cossi M, Cammi R, Mennucci B, Pomelli C, Adamo C, Clifford S, Ochterski J, Petersson G A, Ayala P Y, Cui Q, Morokuma K, Malick D K, Rabuck A D, Raghavachari K, Foresman J B, Cioslowski J, Ortiz J V, Baboul A G, Stefanov B B, Liu G, Liashenko A, Piskorz P, Komaromi I, Gomperts R, Martin R L, Fox D J, Keith T, Al-Laham M A, Peng C Y, Nanayakkara A, Gonzalez C, Challacombe M, Gill P M W, Johnson B G, Chen W, Wong M W, Andres J L, Head-Gordon M, Replogle E S and Pople J A 1998 Gaussian 98, Revision A9, Gaussian, Inc: Pittsburgh, PAGoogle Scholar
  37. 36.
    Foster J P and Weinhold F 1980 J. Am. Chem. Soc. 102 7211CrossRefGoogle Scholar
  38. 37.
    Reed A D, Curtiss L A and Weinhold F 1988 Chem. Rev. 88 899CrossRefGoogle Scholar
  39. 38.
    Glendening E D, Reed A E, Carpenter J E and Weinhold F 1988 NBO 3.1 Program Manual Google Scholar
  40. 39.
    Fukui K 1981 Acc. Chem. Res. 14 363CrossRefGoogle Scholar
  41. 40.
    Gonzalez C and Schlegel H B 1989 J. Chem. Phys. 90 2154CrossRefGoogle Scholar
  42. 41.
    Gonzalez C and Schlegel H B 1990 J. Phys. Chem. 94 5223Google Scholar
  43. 42.
    Wolinski K, Hilton J F and Pulay P 1990 J. Am. Chem. Soc. 112 8251CrossRefGoogle Scholar
  44. 43.
    Keith T A and Bader R F W 1993 Chem. Phys. Lett. 210 223CrossRefGoogle Scholar
  45. 44.
    Keith T A and Bader R F W 1992 Chem. Phys. Lett. 194 1CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 2009

Authors and Affiliations

  • Lakshminarayanan Akilandeswari
    • 1
  • Madhavan Jaccob
    • 1
  • Ponnambalam Venuvanalingam
    • 1
  1. 1.School of ChemistryBharathidasan UniversityTiruchirapalliIndia

Personalised recommendations