Advertisement

Russian Chemical Bulletin

, Volume 56, Issue 2, pp 320–324 | Cite as

Catalytic hydroallylation of norbornadiene with allyl formate

  • I. P. Stolyarov
  • A. E. Gekhman
  • I. I. Moiseev
  • A. Yu. Kolesnikov
  • E. M. Evstigneeva
  • V. R. Flid
Article

Abstract

Norbornadiene (NBD) reacts with allyl esters All—OC(O)R (R = Me, But, Ph, CCl3, CF3) in acetonitrile solutions of palladium(0) complexes to give a mixture of four isomeric nontraditional allylation products and the corresponding carboxylic acids. Under similar conditions, the reaction of NBD with allyl formate in solutions of Pd0 and PdII complexes occurs selectively, resulting in the product of addition of the allyl fragment and the H atom to an NBD double bond, 5-allylbicyclo[2.2.1]hept-2-ene, and CO2. The hydroallylation of NBD is accompanied by catalytic addition of formic and acetic acids to one double bond of the diene to give bicyclo[2.2.1]hept-2-en-5-ol and nortricyclan-3-ol acetates and formates. Unlike most known palladium-based catalyst systems, these complexes exhibit catalytic activity also in the absence of phosphines.

Key words

norbornadiene allylation catalytic hydroallylation palladium(0) complexes palladium(II) complexes allyl esters 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    N. Tsukada, T. Sato, and Y. Inoue, Tetrahedron Lett., 2000, 41, 4181.CrossRefGoogle Scholar
  2. 2.
    E. M. Evstigneeva, O. S. Manulik, and V. R. Flid, Kinet. Katal., 2004, 45, 188 [Kinet. Catal., 2004, 45, 172 (Engl. Transl.)].Google Scholar
  3. 3.
    E. M. Evstigneeva, O. S. Manulik, V. R. Flid, I. P. Stolyarov, N. Yu. Kozitsyna, M. N. Vargaftik, and I. I. Moiseev, Izv. Akad. Nauk. Ser. Khim., 2004, 1292 [Russ. Chem. Bull., Int. Ed., 2004, 53, 1345].Google Scholar
  4. 4.
    N. Yu. Kozitsyna, S. E. Nefedov, M. N. Vargaftik, and I. I. Moiseev, Mendeleev Commun., 2005, 223.Google Scholar
  5. 5.
    N. Yu. Kozitsyna, S. E. Nefedov, N. V. Cherkashina, V. N. Ikorskii, M. N. Vargaftik, and I. I. Moiseev, Izv. Akad. Nauk. Ser. Khim., 2005, 2149 [Russ. Chem. Bull., Int. Ed., 2005, 54, 2215].Google Scholar
  6. 6.
    N. Yu. Kozitsyna, S. E. Nefedov, F. M. Dolgushin, N. V. Cherkashina, M. N. Vargaftik, and I. I. Moiseev, Inorg. Chim. Acta, 2006, 2072.Google Scholar
  7. 7.
    V. R. Flid, O. S. Manulik, A. A. Grigor’ev, and A. P. Belov, Metalloorg. Khim., 1991, 864 [Organomet. Chem. USSR, 1991 (Engl. Transl.)].Google Scholar
  8. 8.
    R. P. Hughes and J. Powell, J. Organomet. Chem., 1973, 60, 387.CrossRefGoogle Scholar
  9. 9.
    J. A. Sadownick and S. J. Lippard, Inorg. Chem., 1973, 12, 2659.CrossRefGoogle Scholar
  10. 10.
    G. M. Bogdanov and A. P. Belov, Zh. Org. Khim., 1977, 13, 932 [J. Org. Chem. USSR, 1977, 13 (Engl. Transl.)].Google Scholar
  11. 11.
    I. I. Moiseev, G. A. Tsirkov, A. E. Gechman, and M. N. Vargaftik, Mendeleev Commun., 1997, 1.Google Scholar
  12. 12.
    S. M. Morehouse, A. R. Powell, J. P. Heffer, T. A. Stephenson, and G. Wilkinson, J. Chem. Soc., 1965, 3632.Google Scholar
  13. 13.
    A. A. Grinberg and L. K. Simonova, Zh. Prikl. Khim., 1953, 26, 880 [J. Appl. Chem. USSR, 1953, 26 (Engl. Transl.)].Google Scholar
  14. 14.
    Y. Tatsuno, T. Yoshida, and Seiotsuka, Inorg. Synth., 1979, 19, 220.CrossRefGoogle Scholar
  15. 15.
    J. R. Doyle, P. E. Slade, and H. B. Jonassen, Inorg. Synth., 1960, 6, 218.Google Scholar
  16. 16.
    Organometallics in Synthesis, Ed. M. Schlosser, Wiley, New York, 1999, 448 pp.Google Scholar

Copyright information

© Springer Science+Business Media, Inc. 2007

Authors and Affiliations

  • I. P. Stolyarov
    • 1
  • A. E. Gekhman
    • 1
  • I. I. Moiseev
    • 1
  • A. Yu. Kolesnikov
    • 2
  • E. M. Evstigneeva
    • 2
  • V. R. Flid
    • 2
  1. 1.N. S. Kurnakov Institute of General and Inorganic ChemistryRussian Academy of SciencesMoscowRussian Federation
  2. 2.M. V. Lomonosov Moscow State Academy of Fine Chemical TechnologyMoscowRussian Federation

Personalised recommendations