Selective Synthesis of Unsymmetrical
Peroxides: Transition-Metal-Catalyzed Oxidation of Malononitrile
and Cyanoacetic Ester Derivatives by tert-Butyl Hydroperoxide
at the α-Position

Alexander O. Terent’ev; Dmitry A. Borisov; Vsevolod V. Semenov; Vladimir V. Chernyshev; Valery M. Dembitsky; Gennady I. Nikishin

doi:10.1055/s-0030-1260027

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Synthesis 2011(13): 2091-2100
DOI: 10.1055/s-0030-1260027

PAPER

Selective Synthesis of Unsymmetrical Peroxides: Transition-Metal-Catalyzed Oxidation of Malononitrile and Cyanoacetic Ester Derivatives by tert-Butyl Hydroperoxide at the α-Position

Alexander O. Terent’ev*^a, Dmitry A. Borisov^a, Vsevolod V. Semenov^a, Vladimir V. Chernyshev^b,c, Valery M. Dembitsky^d, Gennady I. Nikishin*^a
^a N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation
Fax: +7(499)1355328; e-Mail: terentev@ioc.ac.ru;
^b Department of Chemistry, , Moscow State University, 119992 Moscow, Russian Federation
^c A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, 31 Leninsky prosp., 119991 Moscow, Russian Federation
^d Institute for Drug Research, P.O. Box 12065, Hebrew University, Jerusalem 91120, Israel

Further Information

Publication History

Received 2 March 2011
Publication Date:
05 May 2011 (online)

Abstract
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Abstract

A novel method was developed for the selective oxidation of α-monosubstituted malononitrile and cyanoacetic ester derivatives at the α-position based on transition-metal-catalyzed reaction (Cu, Fe, Mn, Co) with tert-butyl hydroperoxide giving unsymmetrical peroxides in 63-94% yields. The method is facile, does not require large excesses of reagents, and is amenable to gram-scale synthesis.

Key words

peroxides - tert-butyl hydroperoxide - catalysis - oxidation - transition metals - malononitrile - cyanoacetic ester

Supporting Information

References

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