Jiang Julong, Ramozzi Romain, Moteki Shin, Usui Asuka, Maruoka Keiji, Morokuma Keiji
Fukui Institute for Fundamental Chemistry, Kyoto University , Takano-Nishihiraki-cho 34-4, Kyoto 606-8103, Japan.
Department of Chemistry, Graduate School of Science, Kyoto University , Kyoto 606-8502, Japan.
J Org Chem. 2015 Sep 18;80(18):9264-71. doi: 10.1021/acs.joc.5b01695. Epub 2015 Sep 9.
The mechanism of the C-H activation of aldehydes and the succeeding acylation of an alkene using a hypervalent iodine reagent is investigated by theoretical calculations. In contrast to the initial proposed mechanism, the present calculations show that the hypervalent iodine is the initiator of the radical reaction. The formation of acyl radical is rate-determining, and the resulting radical acts as the chain carrier. The kinetic isotope effect (KIE) of deuterated aldehyde, as well as other experimental observations, can now be rationalized from the newly proposed mechanism.
通过理论计算研究了使用高价碘试剂实现醛的C-H活化以及随后烯烃的酰化反应的机理。与最初提出的机理不同，目前的计算表明高价碘是自由基反应的引发剂。酰基自由基的形成是速率决定步骤，生成的自由基作为链载体。氘代醛的动力学同位素效应（KIE）以及其他实验观察结果，现在可以从新提出的机理得到合理的解释。
