Skip to main content
SpringerLink
Log in

NBO and NICS analysis of the allylic rearrangements (the Cope and 3-aza-Cope rearrangements) of hexa-1,5-diene and N-vinylprop-2-en-1-amine: A DFT study

  • Research Article
  • Published:
Central European Journal of Chemistry

Abstract

In this work, ab initio density functional theory (DFT) calculations have been performed on the 3,3-sigmatropic rearrangements of hexa-1,5-diene (Cope) and N-vinylprop-2-en-1-amine (3-aza-Cope) in the gas phase. The barrier heights and heats of reactions calculated at the B3LYP/6-311G** level of theory were in good agreement with experimental data. Transition states optimized with B3LYP/6-311G** theory were used for calculating the nucleus independent chemical shift (NICS) and, a natural bond orbital (NBO) analysis was also performed at the same level of theory. Our results indicate that the aromaticities of the transition states are controlled by the out-of-plane component and that the chair-like transition state of the Cope rearrangement exhibits the strongest aromatic character. Analysis of donor-acceptor (bonding and anti-bonding) interactions of σ3–4 → π*1–2 suggests that the TS structure in the hexa-1,5-diene reaction (the Cope rearrangement) has more aromatic character than the N-vinylprop-2-en-1-amine reaction (the 3-aza-Cope rearrangement). The NBO results show that in the hexa-1,5-diene and N-vinylprop-2-en-1-amine rearrangements, activation energies are controlled by σ3–4 → π*1–2 and σ3–4 → π*1–2 resonance energies.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. A.C. Cope, E.M. Hardy, J. Am. Chem. Soc. 62, 441 (1940)

    Article  CAS  Google Scholar 

  2. M. Zora, J. Mol. Struct. (THEOCHEM) 681, 113 (2004)

    Article  CAS  Google Scholar 

  3. F.A. Carey, R.J. Sundberg, Advanced Organic Chemistry, 5th edition (Springer, New York, 2007)

    Google Scholar 

  4. S. Sakai, J. Mol. Struct. (THEOCHEM) 583, 181 (2002)

    Article  CAS  Google Scholar 

  5. V.N. Staroverov, E.R. Davidson, J. Mol. Struct. (THEOCHEM) 573, 81 (2001)

    Article  CAS  Google Scholar 

  6. A.M.M. Castro, Chem. Rev. 104, 2939 (2004)

    Article  CAS  Google Scholar 

  7. P. Merino, T. Tejro, V. Mannucci, Tetrahedron Lett. 48, 3385 (2007)

    Article  CAS  Google Scholar 

  8. R.K. Hill, N.W. Gilman, Tetrahedron. Lett. 8, 1421 (1967)

    Article  Google Scholar 

  9. S. Jolidon, H-J. Hansen, Helv. Chim. Acta. 60, 978 (1977)

    Article  Google Scholar 

  10. M.J. Frisch et al., Gaussian 03, Revision D.01 (Gaussian Inc., Wallingford CT, 2004)

    Google Scholar 

  11. H.B. Schlegel, C. Peng, P.Y. Ayala, M.J. Frisch, J. Comput. Chem. 17, 49 (1996)

    Article  Google Scholar 

  12. S. Glasstone, K.J. Laidler, H. Eyring, The Theory of Rate Processes (McGraw-Hill, New York, 1941)

    Google Scholar 

  13. K.J. Laidler, Theories of Chemical Reaction Rates (McGraw-Hill, New York, 1941)

    Google Scholar 

  14. S.W. Benson, F.R. Cruickshank, D.M. Golden, G.R. Haugen, H.E. O’Neal, A.S. Rodgers, R. Shaw, R. Walsh, Chem. Rev. 69, 279 (1969)

    Article  CAS  Google Scholar 

  15. W.v.E. Doering, V.G. Toscano, G.H. Beasley, Tetrahedron. 27, 5299 (1971)

    Article  CAS  Google Scholar 

  16. M. Hiersemann, U. Nubbemeyer, The Claisen Rearrangement: Methods And Applications (WILEYVCH Verlag GmbH & Co. KGaA, Weinheim, 2007)

    Book  Google Scholar 

  17. N. Agmon, R.D. Levine, Chem. Phys. Lett. 52, 197 (1977)

    Article  CAS  Google Scholar 

  18. P. Cysewski, J. Mol. Struct. (THEOCHEM) 714, 29 (2005)

    Article  CAS  Google Scholar 

  19. P.V.R. Schleyer, C. Maerker, A. Dransfeld, H. Jiao, N.J.R. van Eikema Hommes, J. Am. Chem. Soc. 118, 6317 (1996)

    Article  CAS  Google Scholar 

  20. P.V.R. Schleyer, H. Jiao, B. Goldfuss, P.K. Freeman, Angew. Chem. Int. Ed. Engl. 34, 3337 (1995)

    Google Scholar 

  21. S. Nigam, C. Majumder, S.K. Kulshreshtha, J. Chem. Sci. 118, 575 (2006)

    Article  CAS  Google Scholar 

  22. J.K. Badenhoop, F. Weinhold, Int. J. Quantum Chem. 72, 269 (1999)

    Article  CAS  Google Scholar 

  23. J.E. Carpenter, F. Weinhold, J. Mol. Struct. (THEOCHEM) 169, 41 (1988)

    Article  Google Scholar 

  24. E. Zahedi, M. Aghaie, K. Zare, J. Mol. Struct. (THEOCHEM). 905, 101 (2009)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Chemistry Department, Islamic Azad University, Shahrood Branch P.O.box 36155/133, Shahrood, Iran

    Ehsan Zahedi & Safa Ali-Asgari

  2. Chemistry Department, Shahrood University of Technology, P.O.box 316, Shahrood, Iran

    Vahid Keley

Authors
  1. Ehsan Zahedi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Safa Ali-Asgari
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Vahid Keley
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ehsan Zahedi.

About this article

Cite this article

Zahedi, E., Ali-Asgari, S. & Keley, V. NBO and NICS analysis of the allylic rearrangements (the Cope and 3-aza-Cope rearrangements) of hexa-1,5-diene and N-vinylprop-2-en-1-amine: A DFT study. cent.eur.j.chem. 8, 1097–1104 (2010). https://doi.org/10.2478/s11532-010-0084-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.2478/s11532-010-0084-1

Keywords

Search

Navigation