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Chemical model of oxidases. CuI-catalyzed oxidation of secondary alcohols by dioxygen

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Abstract

Oxidation of secondary alcohols (2-propanol, 2-butanol, and cyclohexanol) by dioxygen, catalyzed by CuI ando-phenanthroline complexes, in the presence of alkali, was studied. The conditions under which oxidative dehydrogenation of secondary alcohols result in fast formation of ketones as the only primary oxidation products were found. Bis-phenanthrolinates [Cu(phen)2]+ are the active forms of the catalyst. The catalytic turnover number for complexes between copper(i) ando-phenanthroline is 1 to 2 s−1 at room temperature.

Kinetic regularities of the reaction are similar to those of the oxidation of alcohols in the presence of oxidases. The mechanism of the process is proposed, suggesting that the oxidation of secondary alcohols occursvia a concerted two-electron mechanism involving a stage of formation of the ternary complex [O2...Cu(phen)2 +...−OCHR1R2]. It is significant for the oxidation mechanism that a hydrogen atom is transferred from the anionic form of a substrate to oxygen, which is confirmed by the value of the kinetic isotope effectk H/k D = 2.1.

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Authors and Affiliations

  1. N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4 ul. Kosygina, 117917, Moscow, Russian Federation

    A. M. Sakharov & I. P. Skibida

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  1. A. M. Sakharov
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  2. I. P. Skibida
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1952–1958, October, 1995.

The work was financially supported by the Russian Foundation for Basic Research (Project No. 94-03-08733a) and the International Science Foundation (Grant MN4 000).

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Sakharov, A.M., Skibida, I.P. Chemical model of oxidases. CuI-catalyzed oxidation of secondary alcohols by dioxygen. Russ Chem Bull 44, 1872–1878 (1995). https://doi.org/10.1007/BF00707215

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  • DOI: https://doi.org/10.1007/BF00707215

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