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Updated: Dec 3, 2025

Achieving Moderate Pressures in Sealed Vessels Using Dry Ice As a Solid CO2 Source
Published on: August 17, 2018
A mechanistic study on Cu(i) catalyzed carboxylation of the C-F bond with CO2: a DFT study
Jiao Liu1, Wan Nie1, Haizhu Yu2
1Hefei National Laboratory for Physical Sciences at the Microscale, iChEM, CAS Key Laboratory of Urban Pollutant Conversion, Anhui Province Key Laboratory of Biomass Clean Energy, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China. shijing@ustc.edu.cn.
Abstract:
The Cu(i) catalyzed carboxylation of the C-F bond recently reported by Yu and co-workers is an excellent method for the construction of complex fluoroacrylate compounds with high regioselectivity. In the present study, theoretical calculations were carried out to investigate the detailed mechanism of the catalytic cycle and the origin of regioselectivity. The calculation results reveal that the overall catalytic cycle proceeds via the migratory insertion of difluoroalkene on the boryl-Cu(i) species, synβ-F elimination, transmetalation, and carboxylation steps. The rate determining step is the carboxylation step, and the migration insertion is the regioselectivity determining step. The regioselectivity for 2,1-insertion is consistent with Yu's experiment, and is determined by both steric and electronic effects.
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