Formic acid reduction. XXIII. Kinetic studies on the formic acid reduction of carbon-carbon double bond adjacent to carbonyl.

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Kinetic manner was introduced into mechanistic studies on the formic acid reduction of carbon-carbon double bond adjacent to carbonyl induced by the formate reagent, TEAF, 5HCO2H·2NEt3. Kinetic data obtained by the use of 1, 3-dimethyl-5-benzyli-denebarbituric acid as a representative, the second order kinetics, the large negative entropy of activation, the isotope effect (2.79) and the positive ρ-value (+1.00) of the Hammett equation, suggest one step path, which proceeds by the attack of HCO2-·HN^+Et3 involving the push-pull mechanism of ring system of a transition state.

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