Chemistry of Heterocyclic Compounds

, Volume 54, Issue 5, pp 520–527 | Cite as

Transition metal-catalyzed C,C- and C,N-cycloaminomethylation reactions of pyrrole and indole

  • Vnira R. Akhmetova
  • El’mira M. Bikbulatova
  • Nail S. Akhmadiev
  • Nailya F. Galimzyanova
  • Raikhana V. Kunakova
  • Askhat G. Ibragimov

Catalytic cycloaminomethylation of pyrrole with bis(methoxymethyl)alkylamines or a mixture of alkyl(phenyl)amines and paraformaldehyde in the presence of [Ni(Py)4Cl2]·0.76H2O or NiCl2·6H2O catalysts proceeded at positions 2 and 5 of pyrrole ring. Cycloaminomethylation of indole was accomplished effectively at positions 1 and 3 in the presence of ZrOCl2·8H2O catalyst. When carbazole was treated with bis(methoxymethyl)alkylamine in the presence of ZrOCl2·8H2O catalyst, it was converted to N-aminomethylated product – N-[(9H-carbazol-9-yl)methyl]-N-(methoxymethyl)alkylamine.


bis(methoxymethyl)alkylamines carbazole indole Lewis acids pyrrole catalysis cycloaminomethylation fungicides heterocyclization 


This work was performed with financial support from the Russian Foundation for Basic Research and the Academy of Sciences of the Bashkortostan Republic (project No. 17-43-020292 r_a) and the project part of the

State Assignment АААА-А117 012610060-7 (2017–2019). Structural characterization of the obtained compounds was performed on the equipment at the Regional Collective Use Center “Agidel”.

Supplementary material

10593_2018_2299_MOESM1_ESM.pdf (1.5 mb)
ESM 1 (PDF 1547 kb)


  1. 1.
    Kaur, R.; Rani, V.; Abbot, V.; Kapoor, Y.; Konar, D.; Kumar, K. J. Pharm. Chem. Chem. Sci. 2017, 1, 17.Google Scholar
  2. 2.
    Roman, G. Mini-Rev. Org. Chem. 2006, 3, 167.CrossRefGoogle Scholar
  3. 3.
    Hsieh, C.-C.; Chao, W.-J.; Horng, Y.-C.; Lee, H. M. J. Chin. Chem. Soc. 2009, 56, 435.CrossRefGoogle Scholar
  4. 4.
    Earle, M. J.; Fairhurst, R. A.; Heaney, H.; Papageorgiou, G.; Wilkins, R. F. Tetrahedron Lett. 1990, 31, 4229.CrossRefGoogle Scholar
  5. 5.
    Heaney, H.; Papageorgiou, G. Tetrahedron 1996, 52, 3473.CrossRefGoogle Scholar
  6. 6.
    Markova, M. V.; Sobenina, L. N.; Ushakov, I. A.; Ivanov, A. V.; Trofimov, B. A. Russ. J. Org. Chem. 2017, 53, 184. [Zh. Org. Khim. 2017, 53, 196.]Google Scholar
  7. 7.
    Khabibullina, G. R.; Zaynullina, F. T.; Valiakhmetova, A. R.; Ibragimov, A. G.; Dzhemilev, U. M. Synthesis 2016, 2294.Google Scholar
  8. 8.
    Khabibullina, G. R.; Fedotova, E. S.; Meshcheryakova, E. S.; Buslaeva, T. M.; Akhmetova, V. R.; Ibragimov, A. G. Chem. Heterocycl. Compd. 2016, 52, 840. [Khim. Geterotsikl. Soedin. 2016, 52, 840.]Google Scholar
  9. 9.
    Akhmetova, V. R.; Akhmadiev, N. S.; Yanybin, V. M.; Galimzyanova, N. F. Russ. J. Org. Chem. 2013, 49, 1072. [Zh. Org. Khim. 2013, 49, 1086.]Google Scholar
  10. 10.
    Akhmetova, V.; Akhmadiev, N. Cascade Amino-, Oxy-, and Thiomethylation of Dicarbonyl СН Acids [in Russian]; Lambert Academic Publishing, 2017, p. 11.Google Scholar
  11. 11.
    Danishefsky, S. J.; Phillips, G. B. Tetrahedron Lett. 1984, 25, 3159.CrossRefGoogle Scholar
  12. 12.
    Microbiology Laboratory [in Russian]; Egorov, N. S., Ed.; Moscow State University: Moscow, 1976, p. 307.Google Scholar
  13. 13.
    Rochin, C.; Babot, O.; Dunoguès, J.; Duboudin, F. Synthesis 1986, 228.Google Scholar
  14. 14.
    (a) Martínez-Mora, E. I.; Caracas, M. A.; Escalante, C. H.; Espinoza-Hicks, C.; Quiroz-Florentino, H.; Delgado, F.; Tamariz, J. Synthesis 2016, 1055. (b) Gurnham, J.; Gambarotta, S.; Korobkov, I.; Jasinska-Walc, L.; Duchateau, R. Organometallics 2014, 33, 4401.Google Scholar
  15. 15.
    Bonev, B.; Hooper, J.; Parisot, J. J. Antimicrob. Chemother. 2008, 61, 1295.CrossRefPubMedGoogle Scholar
  16. 16.
    CrysAlis PRO; Agilent Technologies Ltd.: Yarnton, 2012.Google Scholar
  17. 17.
    Sheldrick, G. M. SHELX, Program for the Refinement of Crystal Structure; Göttingen University: Göttingen, 2008.Google Scholar
  18. 18.
    Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J; Howard, J. A. K., Puschmann, H. J. Appl. Crystallogr. 2009, 42, 339.CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  • Vnira R. Akhmetova
    • 1
  • El’mira M. Bikbulatova
    • 1
  • Nail S. Akhmadiev
    • 1
  • Nailya F. Galimzyanova
    • 2
  • Raikhana V. Kunakova
    • 3
  • Askhat G. Ibragimov
    • 1
  1. 1.Institute of Petrochemistry and CatalysisRussian Academy of SciencesUfaRussia
  2. 2.Institute of Biology, Ufa Science CenterRussian Academy of SciencesUfaRussia
  3. 3.Ufa State Petroleum Technological UniversityUfaRussia

Personalised recommendations