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Russian Chemical Bulletin

, Volume 67, Issue 12, pp 2234–2240 | Cite as

Hydride transfer mechanism in the catalytic allylation of norbornadiene with allyl formate

  • S. A. Durakov
  • R. S. Shamsiev
  • V. R. FlidEmail author
  • A. E. Gekhman
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Abstract

Allylation of norbornadiene with allyl formate in the presence of the palladium catalytic systems is characterized by several peculiarities associated with the new reaction route: hydroallylation (reductive allylation) occurs along with the traditional allylation (oxidative allylation). Both processes are considered from the single point of view, and the mechanism assuming different routes of the hydride transfer in the key intermediates was proposed. It was proved by using deuterated reactants that the hydride transfer can involve the allyl, norbornenyl, or formyl moieties. In all cases, the hydrogen atom bound to the carbon atom in the β-position relative to palladium is eliminated in this step.

Key words

norbornadiene allyl formate allyl acetate palladium acetate allylation hydroallylation homogeneous metallocomplex catalysis hydride transfer 

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References

  1. 1.
    V. R. Flid, M. L. Gringolts, R. S. Shamsiev, E. Sh. Finkelshtein, Russ. Chem. Rev., 2018, 87, 1169.CrossRefGoogle Scholar
  2. 2.
    U. M. Dzhemilev, R. I. Khusnutdinov, G. A. Tolstikov, Russ. Chem. Rev., 1987, 56, 36.CrossRefGoogle Scholar
  3. 3.
    V. R. Flid, Yu. G. Shestova, E. A. Katsman, Kinet. Katal. [Kinet. Catal.], 1992, 33, 223 (in Russian).Google Scholar
  4. 4.
    U. M. Dzhemilev, R. I. Khusnutdinov, D. K. Galeev, O. M. Nefedov, G. A. Tolstikov, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1987, 36, 122.CrossRefGoogle Scholar
  5. 5.
    M. Lautens, W. Tam, in Advances in Metal-Organic Chemistry, Ed. L. S. Liebeskind, JAI Press, Greenwich, 1996, p. 125.Google Scholar
  6. 6.
    V. R. Flid, O. S. Manulik, D. V. Dmitriev, V. B. Kouznetsov, E. M. Evstigneeva, A. P. Belov, A. A. Grigor´ev, Eurasian Chem.-Technol. J., 2001, 3, 73.CrossRefGoogle Scholar
  7. 7.
    E. M. Evstigneeva, R. S. Shamsiev, V. R. Flid, Vestn. MITKhT im. M. V. Lomonosova [Bulletin of M. V. Lomonosov Moscow Institute of Chemical Technology], 2006, No. 1, 3 (in Russian).Google Scholar
  8. 8.
    I. E. Efros, E. M. Evstigneeva, A. A. Kolesnikova, V. R. Flid, Ros. Khim. Zh. [Mendeleev Chem. J.], 2007, 51, 103 (in Russian).Google Scholar
  9. 9.
    N. Tsukada, T. Sato, Y. Inoue, Tetrahedron Lett., 2000, 41, 4181.CrossRefGoogle Scholar
  10. 10.
    E. M. Evstigneeva, O. S. Manulik, V. R. Flid, Kinet. Catal., 2004, 45, 172.CrossRefGoogle Scholar
  11. 11.
    E. M. Evstigneeva, O. S. Manulik, V. R. Flid, I. P. Stolyarov, N. Yu. Kozitsyna, M. N. Vargaftik, I. I. Moiseev, Russ. Chem. Bull., 2004, 53, 1345.CrossRefGoogle Scholar
  12. 12.
    I. P. Stolyarov, A. E. Gekhman, I. I. Moiseev, A. Yu. Kolesnikov, E. M. Evstigneeva, V. R. Flid, Russ. Chem. Bull., 2007, 56, 320.CrossRefGoogle Scholar
  13. 13.
    E. M. Evstigneeva, V. R. Flid, Russ. Chem. Bull., 2008, 57, 837.CrossRefGoogle Scholar
  14. 14.
    V. R. Flid, S. A. Durakov, T. A. Morozova, Russ. Chem. Bull., 2016, 65, 2639.CrossRefGoogle Scholar
  15. 15.
    V. R. Flid, O. S. Manulik, A. P. Belov, A. A. Grigor´ev, Metalloorgan. Khim. [Organomet. Chem.], 1991, 4, 864 (in Russian).Google Scholar
  16. 16.
    J. Tsuji, in Palladium Reagents and Catalysis, John Wiley and Sons, 1996, p. 549.Google Scholar
  17. 17.
    V. R. Flid, S. A. Durakov, Russ. Chem. Bull., 2018, 67, 469.CrossRefGoogle Scholar
  18. 18.
    I. P. Stolyarov, L. I. Demina, N. V. Cherkashina, Russ. J. Inorg. Chem., 2011, 56, 1532.CrossRefGoogle Scholar
  19. 19.
    R. S. Shamsiev, Ha Ngok Thien, V. R. Flid, Russ. Chem. Bull., 2013, 62, 1553.CrossRefGoogle Scholar
  20. 20.
    R. S. Shamsiev, A. V. Drobyshev, V. R. Flid, Russ. J. Org. Chem., 2013, 49, 345.CrossRefGoogle Scholar
  21. 21.
    R. S. Shamsiev, V. R. Flid, Russ. Chem. Bull., 2013, 62, 2301.CrossRefGoogle Scholar
  22. 22.
    Al´ Kh. Khazradzhi, A. V. Krylov, M. V. Kulikova, V. R. Flid, O. Yu. Tkachenko, Tonkie Khim. Tekhnol. [Fine Chemical Technologies], 2016, 11, No. 6, 70 (in Russian).Google Scholar
  23. 23.
    V. R. Flid, S. A. Durakov, T. A. Morozova, D. A. Cheshkov, E. A. Katzman, Russ. Chem. Bull., 2018, 67, 1335.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • S. A. Durakov
    • 1
  • R. S. Shamsiev
    • 1
  • V. R. Flid
    • 1
    Email author
  • A. E. Gekhman
    • 2
  1. 1.MIREA – Russian Technological University, M. V. Lomonosov Institute of Fine Chemical TechnologiesMoscowRussian Federation
  2. 2.N. S. Kurnakov Institute of General and Inorganic ChemistryRussian Academy of SciencesMoscowRussian Federation

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