Skip to main content
SpringerLink
Log in

Reductive allylation of pyrrole with allylboranes. Synthesis oftrans- andcis-2,5-disubstituted pyrrolidines

  • Organic Chemistry
  • Published:
Russian Chemical Bulletin Aims and scope

Abstract

Pyrrole undergoes reductive mono- and diallylation on successive treatment with β,γ-unsaturated organoboron derivatives (triallylborane, allyl(dipropyl)borane, and triprenylborane) and alcohols to give 2-allylated 3-pyrrolines andtrans-2,5-diallylated pyrrolidines. The addition of both the first and second boron-allylic fragment to the heterocycle proceeds with rearrangement. A method for transformation of thetrans-2,5-diallylpyrrolidine into thecis-isomer (heating with triallylborane at 190 °C) was developed and a series ofN-substituted derivatives of these pyrrolidines was synthesized. A method for the preparative synthesis of nonsymmetrically substitutedtrans- andcis-2-alkyl(phenyl)-5-allylpyrrolidines, based on reductive allylboration of pyrrole followed by 1,2-addition of RLi to the 5-allyl-1-pyrroline that formed, was also developed. A direct confirmation of intermediate formation of 2H- and 3H-pyrrole tautomers under the action of allylboranes was obtained. The adduct of 2H-pyrrole with BF3 was detected by NMR spectroscopy.

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. Yu. N. Bubnov, V. C. Bogdanov, and B. M. Mikhailov,Zh. Obshch. Khim., 1968,38, 260 [J. Gen. Chem. USSR, 1968,38 (Engl. Transl.)].

    CAS  Google Scholar 

  2. A. Meller and G. Gerger,Monatsh. Chem., 1974,105, 684.

    Article  CAS  Google Scholar 

  3. R. W. Hoffmann, G. Eichler, and A. Endesfelder,Lieb. Ann. Chem., 1983, 2000.

  4. Y. Yamamoto, S. Nishii, K. Maruyama, T. Kamatsu, and W. Ito,J. Am. Chem. Soc., 1986,108, 7778.

    Article  CAS  Google Scholar 

  5. Y. Yamamoto and N. Asao,Chem. Rev., 1993,93, 2207.

    Article  CAS  Google Scholar 

  6. Yu. N. Bubnov, V. I. Zheludeva, T. Yu. Rudashevskaya, and T. S. Kuznetsova,Izv. Akad. Nauk SSSR, Ser. Khim., 1989, 1179 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1989,38, 1073 (Engl. Transl.)].

    Google Scholar 

  7. L. I. Lavrinovich, A. V. Ignatenko, and Yu. N. Bubnov,Izv. Akad. Nauk, Ser. Khim., 1992, 2597 [Bull. Russ. Acad. Sci., Div. Chem. Sci., 1992,41, 2051 (Engl. Transl.)].

    Google Scholar 

  8. M. E. Gurskii, S. B. Golovin, A. V. Ignatenko, and Yu. N. Bubnov,Izv. Akad. Nauk, Ser. Khim., 1992, 2198 [Bull. Russ. Acad. Sci., Div. Chem. Sci., 1992,41, 1724 (Engl. Transl.)].

    Google Scholar 

  9. Yu. N. Bubnov, S. V. Evchenko, and A. V. Ignatenko,Izv. Akad. Nauk, Ser. Khim., 1992, 2815 [Bull. Russ. Acad. Sci., Div. Chem. Sci., 1992,41, 2239 (Engl. Transl.)].

    Google Scholar 

  10. Yu. N. Bubnov, S. V. Evchenko, and A. V. Ignatenko,Izv. Akad. Nauk, Ser. Khim., 1993, 1325 [Russ. Chem. Bull., 1993,42, 1268 (Engl. Transl.)]:

    Google Scholar 

  11. Yu. N. Bubnov,Izv. Akad. Nauk, Ser. Khim., 1995, 1203 [Russ. Chem. Bull., 1995,44, 1156 (Engl. Transl.)].

  12. Yu. N. Bubnov,Pure Appl. Chem., 1994,66, 235.

    CAS  Google Scholar 

  13. Yu. N. Bubnov, L. I. Lavrinovich, A. Yu. Zykov, E. V. Klimkina, and A. V. Ignatenko,Izv. Akad. Nauk, Ser. Khim., 1993, 1327 [Russ. Chem. Bull., 1993,42, 1269 (Engl. Transl.)].

    Google Scholar 

  14. Yu. N. Bubnov, A. Yu. Zykov, L. I. Lavrinovich, and A. V. Ignatenko,Izv. Akad. Nauk, Ser. Khim., 1993, 1329 [Russ. Chem. Bull., 1993,42, 1271 (Engl. Transl.)].

    Google Scholar 

  15. R. A. Jones, inComprehensive Heterocyclic Chemistry, Eds. A. R. Katritzky and W. Rees, Pergamon Press, Oxford, 1984,4.

    Google Scholar 

  16. A. H. Jackson, inComprehensive Organic Chemistry, Eds. D. Barton and W. D. Ollis, Pergamon Press, Oxford-New York-Toronto-Sydney-Paris-Frankfurt, 1979,4.

    Google Scholar 

  17. R. Köster, H. Bellut, and S. Hauori,Lieb. Ann. Chem., 1968,720, 1.

    Google Scholar 

  18. H. Bellut and R. Koster,Lieb. Ann. Chem., 1970,738, 86.

    CAS  Google Scholar 

  19. R. R. Hill and T. H. Chan,Tetrahedron, 1965,21, 2015.

    Article  CAS  Google Scholar 

  20. Yu. N. Bubnov, E. A. Shagova, S. V. Evchenko, and A. V. Ignatenko,Izv. Akad. Nauk, Ser. Khim., 1994, 693 [Russ. Chem. Bull., 1994,43, 645 (Engl. Transl.)].

    Google Scholar 

  21. Yu. N. Bubnov, E. V. Klimkina, and A. V. Ignatenko,Izv. Akad. Nauk, Ser. Khim., 1998, 467 [Russ. Chem. Bull., 1998,47, 451 (Engl. Transl.)].

  22. Yu. N. Bubnov, E. V. Klimkina, A. V. Ignatenko, and I. D. Gridnev,Tetrahedron Lett., 1997,38, 4631.

    Article  CAS  Google Scholar 

  23. Yu. N. Bubnov, E. V. Klimkina, A. V. Ignatenko, and I. D. Gridnev,Tetrahedron Lett., 1996,37, 1337.

    Article  Google Scholar 

  24. S. M. Bachrach,J. Org. Chem., 1993,58, 5414.

    Article  CAS  Google Scholar 

  25. T. A. Zawodzinski, Jr., L. Janiszewska, and R. A. Osteryoung,J. Electroanal. Chem., 1988,255, 111.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 117913, Moscow, Russian Federation

    Yu. N. Bubnov, E. V. Klimkina, L. I. Lavrinovich, A. Yu. Zykov & A. V. Ignatenko

  2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation

    Yu. N. Bubnov

Authors
  1. Yu. N. Bubnov
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. E. V. Klimkina
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. L. I. Lavrinovich
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. A. Yu. Zykov
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. A. V. Ignatenko
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1718–1728, September, 1999.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Bubnov, Y.N., Klimkina, E.V., Lavrinovich, L.I. et al. Reductive allylation of pyrrole with allylboranes. Synthesis oftrans- andcis-2,5-disubstituted pyrrolidines. Russ Chem Bull 48, 1696–1706 (1999). https://doi.org/10.1007/BF02494816

Download citation

  • Received:

  • Revised:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02494816

Key words

Search

Navigation