N- and C-Vinylation of Pyrroles with Disubstituted Activated Acetylenes

Boris A. Trofimov; Lyubov’ N. Sobenina; Al’bina I. Mikhaleva; Igor A. Ushakov; Tamara I. Vakul’skaya; Zinaida V. Stepanova; Dar’ya-Syren D. Toryashinova; Anastasiya G. Mal’kina; Valentina N. Elokhina

doi:10.1055/s-2003-39411

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N- and C-Vinylation of Pyrroles with Disubstituted Activated Acetylenes

Boris A. Trofimov, Lyubov’ N. Sobenina*, Al’bina I. Mikhaleva, Igor A. Ushakov, Tamara I. Vakul’skaya, Zinaida V. Stepanova, Dar’ya-Syren D. Toryashinova, Anastasiya G. Mal’kina, Valentina N. Elokhina
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street, Irkutsk 664033, Russia
Fax: +7(3952)396046; e-Mail: sobenina@irioch.irk.ru;

Abstract

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Abstract

Addition of pyrrole and 2-phenylpyrrole to 2-acyl- and 2-cyano-1-phenylacetylenes in the KOH-DMSO system affords chemo- and regioselectively N-adducts: 1-(2-acyl- and 1-(2-cyano-1-phenylethenyl)pyrroles in 32-89% yield. 4,5,6,7-Tetrahydroindole reacts with 2-cyano-1-phenylacetylene analogously. Unexpectedly, with 2-benzoyl-1-phenylacetylene, the reaction follows mainly the C-vinylation route to give (E,Z)-2-(2-benzoyl-1-phenylethenyl)-4,5,6,7-tetrahydroindole and cyclo-bis-adduct, 2-(2-benzoyl-1,3-diphenyl-1,4,5,6,7,8-hexahydrocyclopenta[b]indol-1-yl)-1-phenylethanone, a product of intramolecular cyclization of 2,3-di(2-benzoyl-1-phenylethenyl)-4,5,6,7-tetrahydroindole.

Key words

pyrroles - alkynes - alkenation - chemoselectivity - regioselectivity - cyclizations - indoles

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References

1 Gossauer A. Die Chemie der Pyrrole Springer-Verlag; Berlin: 1974.

2 Jones RA. Bean GP. The Chemistry of Pyrroles Academic Press; London: 1977.

3 Trofimov BA. The Chemistry of Heterocyclic Compounds. Pyrroles. Wiley; New York: 1992.

4 Sobenina LN. Demenev AP. Mikhaleva AI. Trofimov BA. Uspekhi Khimii (Russian Chemical Reviews) 2002, 71: 641

5 Trofimov BA. Mikhaleva AI. N-Vinylpyrroles (in Russian) Nauka; Novosibirsk: 1984. Chem. Abstr. 1985, 102, 203864

6 Trofimov BA. Vinylpyrroles, In Pyrroles. Part Two. The Synthesis, Reactivity, and Physical Properties of Substituted Pyrroles Jones RA. Interscience Publication, Wiley; New-York: 1992.

7 Trofimov BA. Stepanova ZV. Sobenina LN. Ushakov IA. Elokhina VN. Mikhaleva AI. Vakul’skaya TI. Toryashinova D.-SD. Mendeleev Commun. 1998, 119

8 Trofimov BA. Stepanova ZV. Sobenina LN. Mikhaleva AI. Vakul’skaya TI. Elokhina VN. Ushakov IA. Toryashinova D.-SD. Kositsyna EI. Izv. Akad. Nauk. Ser. Khim. 1999, 1562

9 Chipanina NN. Stepanova ZV. Gavrilova GA. Sobenina LN. Mikhaleva AI. Izv. Akad. Nauk. Ser.Khim. 2000, 1945

10 Trofimov BA. Stepanova ZV. Sobenina LN. Mikhaleva AI. Ushakov IA. Toryashinova D.-SD. Khim. Geterotsicl. Soedin. 1999, 1253

11 Trofimov BA. Stepanova ZV. Sobenina LN. Mikhaleva AI. Ushakov IA. Elokhina VN. Synthesis 2001, 1878

12 Peglow T. Blechert S. Steckhan E. Chem.-Eur. J. 1998, 107

13 Mal’kina AG. Skvortsov YuM. Trofimov BA. Toryashinova D.-SD. Chipanina NN. Volkov AN. Keiko VV. Proidakov AG. Aksamentova TN. Domnina ES. Zh. Org. Khim. 1981, 17: 2438

14 Skvortsov YuM. Mal’kina AG. Trofimov BA. Volkov AN. Glaskova NP. Proidakov AG. Zh. Org. Khim. 1982, 18: 983

15 Kumar A. Nagayama K. Ernst RR. J. Magn. Reson. 1980, 40: 321

16 Jeener J. Meier BH. Ernst RR. J. Chem. Phys. 1979, 69: 4546

17 Poole CP. Electron Spin Resonance. A Comprehensive Treatise on Experimental Techniques 2nd ed.: Wiley-Interscience; New York: 1983.

18 Trofimov BA. Preparation of Pyrroles from Ketoximes and Acetylene, In Adv. Heterocycl. Chem. Vol. 51: Katritzky AR. Academic Press; San Diego: 1990. p.177

19 Tedeschi RJ. Acetylene, In Encyclopedia of Physical Science and Technology Vol. 1: Academic Press; San Diego: 1992. p.27

20 Bean GP. The Synthesis of 1H-Pyrroles, In Pyrroles. Part One. The Synthesis and the Chemical and the Physical Aspects of Pyrrole Ring Jones RA. Interscience Publication, Wiley; New York: 1992.

21 Varlamov AB. Borisova TN. Voskressensky LG. Synthesis 2002, 155