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J Org Chem. 2005 Apr 15;70(8):3140-7.

Oxidative formation of thiolesters in a model system of the pyruvate dehydrogenase complex.

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Department of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo, Meguro-ku, Tokyo 153-8902, Japan.


In the presence of a catalytic amount of 3-butyl-4-methylthiazolium bromide, the reaction of benzaldehydes with azobenzene in dichloromethane containing octanethiol and Et(3)N gave the corresponding S-octyl thiobenzoates in good yields. The thiolesters were produced by trapping of the 2-benzoylthiazolium salts with the thiol, which were generated through the azobenzene oxidation of the active aldehydes. This is the first example for the thiolester formation mimicking the function of the pyruvate dehydrogenase complex. An electron-withdrawing substituent at the 4-position of benzaldehyde enhanced the reaction rate. The effect of benzaldehyde substituents on the reaction rate was examined quantitatively on the basis of kinetic measurements, leading to a nonlinear correlation of log(k(obs)) with Hammett's substituent constants (sigma). The origin of the nonlinear Hammett plot was interpreted in terms of a shift in the rate-determining step of the multistep reaction with change of the electronic nature of substituent. Further support for this assumption was given by the observation that the reaction constant (rho) of the Hammett plot for the azobenzene substituent effect on the oxidation rate of 4-bromobenzaldehyde was much smaller than that of 4-cyanobenzaldehyde.

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