Skip to main content
SpringerLink
Log in

Diels–Alder reactivity of benzannulated isobenzofurans as assessed by density functional theory

  • Original Paper
  • Published:
Journal of Molecular Modeling Aims and scope Submit manuscript

Abstract

Density functional theory (DFT) calculations at the B3LYP/6-31G* level for isobenzofuran 1 and eleven benzannulated derivatives of types 2 and 3 have been performed in order to compare their relative reactivities as dienes in Diels–Alder reactions. The transition state (TS) energies for their reactions with ethylene have been determined and shown to form a linear correlation between activation energies and structure count (SC) ratios. TS energies as a method for comparison of diene reactivities can be applied to IBFs bearing substituents on the ring as well as those containing heteroatoms, for which the SC ratio method failed. Different measures of aromaticity of benzannulated IBFs indicated a decrease in aromaticity going from 4 to 14, which is also reflected in their reactivity as a dienes in Diels–Alder reaction.

Figure Isobenzofuran 1 and benzannulated isobenzofurans 2 and 3

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

Fig. 1.
Fig. 2.
Fig. 3.
Fig. 4.
Fig. 5.
Fig. 6.
Fig. 7.
Fig. 8.
Fig. 9.
Fig. 10.

Similar content being viewed by others

References

  1. Friedrichsen W (1999) Adv Heterocycl Chem 73:1–96

    CAS  Google Scholar 

  2. Peters O, Friedrichsen W (1995) Trends Heterocycl Chem 4:217–228

    CAS  Google Scholar 

  3. Wiersum UE (1981) Aldrichimica Acta 14:53–58

    CAS  Google Scholar 

  4. Friedrichsen W (1980) Adv Heterocycl Chem 26:135–241

    CAS  Google Scholar 

  5. Haddadin MJ (1978) Heterocycles 9:865–901

    CAS  Google Scholar 

  6. See for instance Warrener RN, Wang S, Butler DN, Russell RA (1997) Synlett 44–46

  7. Warrener RN, Wang S, Russell RA, Gunter MJ (1997) Synlett 47–50

  8. Warrener RN, Wang S, Butler DN, Russell RA (1997) Tetrahedron 53:3975–3990

    Google Scholar 

  9. Smith JG, Dibble PW, Sandborn RE (1983) J Chem Soc Chem Commun 1197–1198

  10. Dibble PW, Rodrigo R (1988) Org Mass Spectrom 23:743–750

    CAS  Google Scholar 

  11. Moursounidis J, Wege D (1988) Aust J Chem 41:235–249

    CAS  Google Scholar 

  12. Tu NPW, Yip JC, Dibble PW (1996) Synthesis 77–81

  13. Juršić BS (1995) J Chem Soc Perkin Trans 2 1217–1222

    Google Scholar 

  14. Juršić BS (1997) Tetrahedron 53:13285 −13294

    Google Scholar 

  15. Juršić BS (1996) J Heterocycl Chem 33:1079–1081

    Google Scholar 

  16. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Zakrzewski VG, Montgomery Jr. JA, Stratmann RE, Burant JC, Dapprich S, Millam JM, Daniels AD, Kudin KN, Strain MC, Farkas O, Tomasi J, Barone V, Cossi M, Cammi R, Mennucci B, Pomelli C, Adamo C, Clifford S, Ochterski J, Petersson GA, Ayala PY, Cui Q, Morokuma K, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Cioslowski J, Ortiz JV, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Gomperts R, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Gonzalez C, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Andres JL, Gonzalez C, Head-Gordon M, Replogle ES, Pople JA (1998) Gaussian 98, Revision A.5. Gaussian, Pittsburgh, Pa.

  17. Becke AD (1993) J Chem Phys 98:1372–1377

    CAS  Google Scholar 

  18. Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785–789

    Article  CAS  Google Scholar 

  19. Herndon WC (1975) J Org Chem 40:3583–3586

    CAS  Google Scholar 

  20. Pearson RG (1989) J Org Chem 54:1432–1435

    Google Scholar 

  21. Zhou Z, Parr RG (1989) J Am Chem Soc 111:7371–7379

    CAS  Google Scholar 

  22. Bean GP (1998) J Org Chem 63:2497–2506

    Article  CAS  PubMed  Google Scholar 

  23. Katritzky AR, Barczynski P, Musumarra G, Pisano D, Szafran M (1989) J Am Chem Soc 111:7–15

    CAS  Google Scholar 

  24. Scott AP, Agranat I, Biedermann PU, Riggs NV, Radom L (1997) J Org Chem 62:2026–2038

    Article  CAS  PubMed  Google Scholar 

  25. Juršić BS (1999) Theochem 468:171–179

    Article  Google Scholar 

  26. Manoharan M, De Proft F, Geerlings P (2000) J Chem Soc Perkin 2 8:1767–1773

    Google Scholar 

  27. Subramanian G, Schleyer PvR, Jiao H (1996) Angew Chem, Int Ed Engl 35:2638–2641

  28. Juršić BS (1998) Theochem 427:165–169

    Article  Google Scholar 

  29. Gugelchuk MM, Chan PCM, Sprules TJ (1994) J Org Chem 59:7723–7731

    CAS  Google Scholar 

  30. Hammond GS (1955) J Am Chem Soc 77:334–338

    CAS  Google Scholar 

Download references

Acknowledgments

We thank the Australian Research Council (ARC) for funding.

Author information

Authors and Affiliations

  1. Centre for Molecular Architecture, Central Queensland University, 4701, North Rockhampton, Queensland, Australia

    Davor Margetić & Ronald N. Warrener

  2. Department of Chemistry, University of Lethbridge, Lethbridge, AB T1K 3M4, Canada

    Peter W. Dibble

Authors
  1. Davor Margetić
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ronald N. Warrener
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Peter W. Dibble
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Davor Margetić.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Margetić, D., Warrener, R.N. & Dibble, P.W. Diels–Alder reactivity of benzannulated isobenzofurans as assessed by density functional theory. J Mol Model 10, 87–93 (2004). https://doi.org/10.1007/s00894-003-0143-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00894-003-0143-z

Keywords

Search

Navigation