Mechanism of Metal-Free C-H Activation of Branched Aldehydes and Acylation of Alkenes Using Hypervalent Iodine Compound: A Theoretical Study

The Journal of Organic Chemistry
Julong JiangKeiji Morokuma

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.

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Citations

Oct 24, 2017·Chemistry : a European Journal·Minh Duy VuXue-Wei Liu
Oct 9, 2018·Angewandte Chemie·Samantha RoheLouis Barriault
Jul 30, 2019·ChemSusChem·Ioanna K SideriChristoforos G Kokotos
Dec 2, 2017·Chemistry : a European Journal·Giorgos N PapadopoulosChristoforos G Kokotos
Sep 21, 2017·Angewandte Chemie·Satobhisha MukherjeeFrank Glorius
Nov 20, 2020·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Akira MatsumotoKeiji Maruoka
Jun 12, 2021·Chemical Communications : Chem Comm·Yi-Lin LiuWen-Ting Wei
Jul 21, 2021·Organic & Biomolecular Chemistry·Yusuke KobayashiYoshiji Takemoto
Jan 21, 2020·ACS Omega·Hasil AmanGary Jing Chuang
Sep 30, 2021·Chemical Reviews·Natalie Holmberg-Douglas, David A Nicewicz

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