Skip to main content
SpringerLink
Log in

Cycloaddition of [3]dendralene derivatives to dinitrobenzofuroxan and nitrobenzodifuroxan

  • Published:
Chemistry of Heterocyclic Compounds Aims and scope

Abstract

It has been shown experimentally (by NMR spectroscopy and X-ray structural analysis) and theoretically (by quantum-chemical calculations according to DFT with B3LYP/6-31G* basis set) that the cycloaddition of [3]dendralene derivatives to nitrobenzodifuroxan and dinitrobenzofuroxan occurs by a stepwise mechanism with a σ-complex as intermediate. It was shown that the cycloaddition steps occurring contrary to the Alder endo rule are characterized by significant global electrophilicity index differences for the reagents (Δω > 3.0 eV). The stages with Δω ≤ 3.0 eV occurred in accordance with the Alder endo rule as concerted processes. X-ray structural analysis and quantum-chemical calculations within the framework of AIM model identified intramolecular attraction forces between non-bonded atoms in the cycloadduct of phenyldendralene and nitrobenzodifuroxan.

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

Scheme 1
Scheme 2
Figure 1
Scheme 3
Figure 2
Figure 3
Scheme 4
Figure 4
Scheme 5
Scheme 6
Figure 5
Scheme 7

Similar content being viewed by others

Notes

  1. Some cases of Alder endo rule violation as a result of stepwise mechanism of cycloaddition have been considered in the literature18.

  2. Two different stable conformers of σ-complex were formed by rotation around the formally single С–С bonds (shown for the case of structure 19, Scheme 6).

References

  1. Tattje, D. H. E.; Bos, R.; Bruins, A. P. Planta Med. 1980, 38, 79.

    Article  CAS  Google Scholar 

  2. Arnone, A.; Cardillo, R.; Di Modugno, V.; Nasini, G. J. Chem. Soc., Perkin Trans. 1 1989, 1995.

  3. Nagase, R.; Katayama, M.; Mura, H.; Matsuo, N.; Tanabe, Y. Tetrahedron Lett. 2008, 49, 4509.

    Article  CAS  Google Scholar 

  4. Bonnett, R.; Davies, J. E.; Hursthouse, M. B. Nature 1976, 262, 326.

    Article  CAS  Google Scholar 

  5. Bojase, G.; Nguyen, T. V.; Payne, A. D.; Willis, A. C.; Sherburn, M. S. Chem. Sci. 2011, 2, 229.

    Article  CAS  Google Scholar 

  6. Iyoda, M.; Nakamura, N.; Todaka, M.; Ohtsu, S.; Hara, K.; Kuwatani, y.; Yoshida, M.; Matsuyama, H., Sugita, M; Tachibana, H.; Inoue, H. Tetrahedron Lett. 2000, 41, 7059.

  7. Hopf, H.; Sherburn, M. S. Angew. Chem., Int. Ed. 2012, 51, 2298.

    Article  CAS  Google Scholar 

  8. Tsuge, O.; Wada, E.; Kanemasa, S.; Sakon, H. Bull. Chem. Soc. Jpn. 1984, 57, 3221.

    Article  CAS  Google Scholar 

  9. Kurbatov, S.; Goumont, R.; Marrot, J.; Terrier, F. Tetrahedron Lett. 2004, 45, 1037.

    Article  CAS  Google Scholar 

  10. Kurbatov, S.; Goumont, R.; Lakhdar, S.; Marrot, J.; Terrier, F. Tetrahedron Lett. 2005, 61, 8167.

    Article  CAS  Google Scholar 

  11. Kurbatov, S.; Lakhdar, S., Goumont, R.; Terrier, F. Org. Prep. Proced. Int. 2012, 44, 289.

    Article  CAS  Google Scholar 

  12. Sepulcri, P.; Halle, J.-C.; Goumont, R.; Riou, D.; Terrier, F. J. Org. Chem. 1999, 64, 9254.

    Article  CAS  Google Scholar 

  13. (a) Buncel, E.; Terrier, F. Org. Biomol. Chem. 2010, 8, 2285. (b) Terrier, F.; Dust, J. M.; Buncel, E. Tetrahedron. 2012, 68, 1829.

  14. Terrier, F.; Kizilian, E.; Halle, J.-C.; Buncel, E. J. Am. Chem. Soc. 1992, 114, 1740.

    Article  CAS  Google Scholar 

  15. Goumont, R.; Sebban, M.; Sepulcri, P.; Marrot, J.; Terrier, F. Tetrahedron 2002, 58, 3249.

    Article  CAS  Google Scholar 

  16. Steglenko, D. V.; Kletsky, M. E.; Kurbatov, S. V.; Tatarov, A. V.; Minkin, V. I.; Goumont, R.; Terrier, F. Chem.–Eur. J. 2011, 17, 7592.

  17. Lakhdar, S.; Terrier, F.; Vichard, D.; Berionni, G.; El Guesmi, N.; Boubaker, T.; Goumont, R. Chem.–Eur. J. 2010, 16, 5681.

  18. García, J. I.; Mayoral, J. A.; Salvatella, L. Acc. Chem. Res. 2000, 33, 658.

    Article  Google Scholar 

  19. Parr, R. G.; von Szentpaly, L.; Liu, S. J. Am. Chem. Soc. 1999, 121, 1922.

    Article  CAS  Google Scholar 

  20. Parr, R. G.; Yang, W. Density Functional Theory of Atoms and Molecules; Oxford University Press: New York, 1989.

    Google Scholar 

  21. Bradford, T. A.; Payne, A. D.; Willis, A. C.; Paddon-Row, M. N.; Sherburn, M. S. J. Org. Chem. 2010, 75, 491.

    Article  CAS  Google Scholar 

  22. Lyssenko, K. A.; Antipin, M. Yu.; Antonov, D. Yu. ChemPhysChem 2003, 4, 817.

    Article  CAS  Google Scholar 

  23. Bader, R. Atoms in Molecules. A Quantum Theory [Russian translation]; Mir: Moscow, 2001.

  24. Lyssenko, K. A. Mendeleev Commun. 2012, 22, 1.

    Article  CAS  Google Scholar 

  25. Munoz, E.; Benito, A. M.; Estepa, L. C.; Fernandez, J.; Maniette, Y.; Martinez, M. T.; de la Fuente, G. F.; Liu, H.; Silva, C. M.; Macedo, E. A.; Espinosa, E.; Molins, E.; Lecomte, C. Chem. Phys. Lett. 1998, 285, 170.

    Article  Google Scholar 

  26. Espinosa, E.; Alkorta, I.; Rozas, I.; Elguero, J.; Molins, E. Chem. Phys. Lett., 2001, 336, 457.

    Article  CAS  Google Scholar 

  27. Minkin, V. I.; Tkachuk, A. V.; Kletskii, M. E.; Steglenko, D. V.; Voronina, V. A.; Kurbatov S. V. Russ. Chem. Bull. 2013, 62, 464. [Izv. Akad. Nauk, Ser. Khim. 2013, 2, 464.]

  28. Gilli, G.; Bellucci, F.; Ferretti, V.; Bertolasi, V. J. Am. Chem. Soc. 1989, 111, 1023.

    Article  CAS  Google Scholar 

  29. Gilli, P.; Bertolasi, V.; Ferretti, V.; Gilli, G. J. Am. Chem. Soc. 1994, 116, 909.

    Article  CAS  Google Scholar 

  30. Guben-Veil' Methods of Organic Chemistry. Vol 2. Methods of Analysis [Russian translation], Goskhimizdat: Мoscow, 1963, pp 103–109.

  31. Gilli, P.; Gilli, G. J. Mol. Struct. 2000, 552, 1.

    Article  CAS  Google Scholar 

  32. Bailey, A. S.; Case, J. R. Tetrahedron 1958, 3, 113.

    Article  CAS  Google Scholar 

  33. Drost, P. Justus Liebigs Ann. Chem. 1899, 307, 49.

    Article  CAS  Google Scholar 

  34. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A.; Vreven, T., Jr.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; 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, J. E., Hratchian, H. P.; 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.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, J. D.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Gaussian, Inc.: Wallingford, 2004.

  35. Lyssenko, K. A.; Antipin, M. Yu. Russ. Chem. Bull. 2006, 55, 1. [Izv. Akad. Nauk, Ser. Khim. 2006, 1.]

  36. Bader, R. F. W. Atoms in Molecules. A Quantum Theory; Clarendon Press: Oxford, 1990.

    Google Scholar 

  37. Sheldrick, G. M. Acta Crystallogr., Sect. A: Found. Crystallogr. 2008, A64,

Download references

This study was supported by a Russian Scietific Fund grant (project 14-13-00103).

Author information

Authors and Affiliations

  1. Southern Federal University, 7 Zorge St., Rostov-on-Don, 344090, Russia

    Pavel G. Morozov, Sergey V. Kurbatov, Yulia P. Semenyuk, Oleg N. Burov, Mikhail E. Kletskii, Nikita S. Fedik & Konstantin F. Suzdalev

Authors
  1. Pavel G. Morozov
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Sergey V. Kurbatov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yulia P. Semenyuk
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Oleg N. Burov
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Mikhail E. Kletskii
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Nikita S. Fedik
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Konstantin F. Suzdalev
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Pavel G. Morozov.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Morozov, P.G., Kurbatov, S.V., Semenyuk, Y.P. et al. Cycloaddition of [3]dendralene derivatives to dinitrobenzofuroxan and nitrobenzodifuroxan. Chem Heterocycl Comp 51, 903–912 (2015). https://doi.org/10.1007/s10593-015-1794-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10593-015-1794-2

Keywords

Search

Navigation