Issue 10, 2012
From the journal:

RSC Advances

Electrocatalysis in MIRC reaction strategy: facile stereoselective approach to medicinally relevant spirocyclopropylbarbiturates from barbituric acids and activated olefins†

Evgeniya O. Dorofeeva,*a   Michail N. Elinson,a   Anatoly N. Vereshchagin,a   Nikita O. Stepanov,a   Ivan S. Bushmarinov,b   Pavel A. Belyakov,a   Olga O. Sokolovaa  and  Gennady I. Nikishina  

* Corresponding authors

a N. D. Zelinsky Institute of Organic Chemistry, Leninsky pr. 47, Moscow, Russian Federation
E-mail: e.o.dorofeeva@gmail.com
Fax: +7(499)1355328
Tel: +7(499)1372944

b A. N. Nesmeyanov Institute of Organoelement Compounds, Vavilova str. 28, Moscow, Russian Federation
E-mail: ib@ineos.ac.ru
Fax: +7(499)1355085
Tel: +7(499)1359202

Abstract

The combined electrolysis of barbituric acids and benzylidenemalononitriles or benzylidenecyanoacetates in methanol in an undivided cell in the presence of sodium bromide results in efficient MIRC (Michael-initiated ring-closure) formation of the corresponding spirocyclopropylbarbiturates in 45–93% yield. The electrocatalytic reaction proceeds smoothly under neutral and mild conditions with benzylidenemalononitriles or benzylidenecyanoacetates bearing both electron-donating and electron-withdrawing groups. NMR and single X-ray diffraction studies indicate that the electrocatalytic MIRC transformation of barbituric acids and benzylidenecyanoacetates results in the stereoselective formation of spirocyclopropanes with an (E)-configuration of aryl and alkoxycarboxylate substituents. The implication of electrocatalysis in the MIRC reaction strategy allows the combination of the synthetic virtues of both methods and accounts for an efficient approach to medicinally relevant spirocyclopropylbarbiturates avoiding inconvenient direct use of molecular halogen or halogenated substrates in accordance with the concepts of modern green chemistry.

Graphical abstract: Electrocatalysis in MIRC reaction strategy: facile stereoselective approach to medicinally relevant spirocyclopropylbarbiturates from barbituric acids and activated olefins

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Article information

DOI
https://doi.org/10.1039/C2RA20078C
Article type
Paper
Submitted
13 Jan 2012
Accepted
16 Mar 2012
First published
20 Mar 2012

RSC Adv., 2012,2, 4444-4452

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Electrocatalysis in MIRC reaction strategy: facile stereoselective approach to medicinally relevant spirocyclopropylbarbiturates from barbituric acids and activated olefins

E. O. Dorofeeva, M. N. Elinson, A. N. Vereshchagin, N. O. Stepanov, I. S. Bushmarinov, P. A. Belyakov, O. O. Sokolova and G. I. Nikishin, RSC Adv., 2012, 2, 4444 DOI: 10.1039/C2RA20078C

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