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Updated: Mar 26, 2026

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Mechanism of iridium-catalysed branched-selective hydroarylation of vinyl ethers: a computational study
1Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, P.R. China. gphuang@tju.edu.cn.
Abstract:
The iridium-catalysed branched-selective hydroarylation of vinyl ethers represents a rare example of the branched-selective hydroarylation involving the non-styrene-type alkenes. Herein, we report our DFT calculations on the mechanism of this reaction. The results show that after C-H oxidative addition, instead of the widely accepted Chalk-Harrod type mechanism, the branched-selective hydroarylation may proceed through an unconventional modified Chalk-Harrod type mechanism, involving the migratory insertion into the Ir-C bond and C-H reductive elimination. Both steric and electronic effects of the alkoxy group were found to account for the complete branched selectivity.
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