Issue 14, 2007
From the journal:

Organic & Biomolecular Chemistry

Oxidation of some cage hydrocarbons by dioxiranes. Nature of the transition structure for the reaction of C–H bonds with dimethyldioxirane: a comparison of B3PW91 density functional theory with experiment†

Stanislav A. Grabovskiy,*a   Arcadiy V. Antipin,a   Elena V. Ivanova,b   Vladimir A. Dokichev,a   Yuriy V. Tomilovc  and  Natalie N. Kabal'novaa  

* Corresponding authors

a Institute of Organic Chemistry, Ufa Research Centre of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054 Ufa, Russia
E-mail: stas_g@anrb.ru, stas_g@isof.cnr.it

b Centre for Research in Molecular Modeling, and Department of Chemistry and Biochemistry, Concordia University, 7141 Sherbrooke St. West, Montréal, Québec, Canada

c N. D. Zelinsky Institute of Organic Chemistry, 47 Leninsky prospect, 117913 Moscow, Russia

Abstract

Dimethyl- (DMD) and methyl(trifluoromethyl)-dioxiranes were used for oxyfunctionalization of spiro{1′,7-cyclopropan-(E)-2-methylbicyclo[2.2.1]heptane} (1), tricyclo[3.2.2.02,4]nonane (2), exo-endo-endo- (3) and exo-exo-exo- (4) heptacyclo[9.3.1.02,10.03,8.04,6.05,9.012,14]pentadecane, yielding tertiary alcohols as the main products. The rate constants for oxidation of 1–4 by DMD were measured and the Arrhenius parameters determined. The DFT theory (B3LYP and B3PW91) using restricted and unrestricted methods was employed to study the oxidation reaction of the C–H bond of cage hydrocarbons 1–4, adamantane, and acetone with DMD. The kinetic isotopic effect calculated using unrestricted methods agreed with experiment. The reaction mechanism in terms of the concerted oxygen insertion vs. the radical part is discussed.

Graphical abstract: Oxidation of some cage hydrocarbons by dioxiranes. Nature of the transition structure for the reaction of C–H bonds with dimethyldioxirane: a comparison of B3PW91 density functional theory with experiment

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Article information

DOI
https://doi.org/10.1039/B707753J
Article type
Paper
Submitted
22 May 2007
Accepted
24 May 2007
First published
14 Jun 2007

Org. Biomol. Chem., 2007,5, 2302-2310

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Oxidation of some cage hydrocarbons by dioxiranes. Nature of the transition structure for the reaction of C–H bonds with dimethyldioxirane: a comparison of B3PW91 density functional theory with experiment

S. A. Grabovskiy, A. V. Antipin, E. V. Ivanova, V. A. Dokichev, Y. V. Tomilov and N. N. Kabal'nova, Org. Biomol. Chem., 2007, 5, 2302 DOI: 10.1039/B707753J

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