Kinetics and Mechanism of the Oxidative Cleavage of Unsaturated Acids by Quinolinium Dichromate

Article abstract of DOI:10.1246/bcsj.67.2320

Quinolinium dichromate (QDC) oxidizes cinnamic and crotonic acids smoothly in N,N-dimethylformamide in the presence of an acid.The reaction has a unit dependence on each of the substrate, oxidant, and acid concentrations.The mechanistic pathway involves an electrophilic attack of the oxidant on the double bond of the substrate, giving a carbonium-ion intermediate.This is supported by a small inverse kinetic isotope effect (k_H/k_D = 0.78) at the α-carbon and the value of ρ = -4.0.