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Synthesis 2011(18): 3015-3019  
DOI: 10.1055/s-0030-1261031
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Stereoselective Electrocatalytic Cyclization of 4,4′-(Arylmethylene)bis(1H-pyrazol­-5-ols) to (5R*,6R*)-11-Aryl-4,10-dimethyl-2,8-diphenyl-2,3,8,9-tetraazadispiro[4.0.4.1]undeca-3,9-diene-1,7-diones

Michail N. Elinson*a, Anatolii N. Vereshchagina, Evgeniya O. Tretyakovaa, Ivan S. Bushmarinovb, Gennady I. Nikishina
a N. D. Zelinsky Institute of Organic Chemistry, Leninsky pr. 47, Moscow, 119991, Russian Federation
Fax: +7(499)1355328; e-Mail: elinson@ioc.ac.ru;
b A. N. Nesmeyanov Institute of Organoelement Compounds, Vavilova str. 28, Moscow, 119991, Russian Federation
Fax: +7(499)1355085; e-Mail: ib@ineos.ac.ru;
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Publikationsverlauf

Received 10 May 2011
Publikationsdatum:
08. August 2011 (online)

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Abstract

Indirect electrochemical oxidation of 4,4′-(arylmethylene)bis(1H-pyrazol-5-ols) in methanol in an undivided cell in the presence of sodium bromide results in highly efficient formation of the corresponding bis(spiro-2,4-dihydro-3H-pyrazol-3-one)cyclopropanes with 85-96% substance yields and 70-80% current efficiency. NMR and single crystal X-ray diffraction indicate that the products are formed exclusively as (R*,R*)-isomers. The application of this effective indirect electrochemical approach to the corresponding pharmacologically promising bis(spiro-2,4-dihydro-3H-pyrazol-3-one)cyclopropanes allows facile and convenient reaction conditions, and is valuable from the viewpoint of environmentally benign synthesis and large-scale processes.

Key words

electrochemistry - spiro compounds - pyrazolone - cyclopropane - diastereoselectivity

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