title: Mechanism of Metal-Free C-H Activation of Branched Aldehydes and Acylation of Alkenes Using Hypervalent Iodine Compound: A Theoretical Study.
abstract: 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.
authors: Fukui Institute for Fundamental Chemistry, Kyoto University , Takano-Nishihiraki-cho 34-4, Kyoto 606-8103, Japan.
authors: Julong
authors: J
authors: Jiang
authors: Fukui Institute for Fundamental Chemistry, Kyoto University , Takano-Nishihiraki-cho 34-4, Kyoto 606-8103, Japan.
authors: Romain
authors: R
authors: Ramozzi
authors: Department of Chemistry, Graduate School of Science, Kyoto University , Kyoto 606-8502, Japan.
authors: Shin
authors: S
authors: Moteki
authors: Department of Chemistry, Graduate School of Science, Kyoto University , Kyoto 606-8502, Japan.
authors: Asuka
authors: A
authors: Usui
authors: Department of Chemistry, Graduate School of Science, Kyoto University , Kyoto 606-8502, Japan.
authors: Keiji
authors: K
authors: Maruoka
authors: Fukui Institute for Fundamental Chemistry, Kyoto University , Takano-Nishihiraki-cho 34-4, Kyoto 606-8103, Japan.
authors: Keiji
authors: K
authors: Morokuma