A mechanistic study on Cu(I) catalyzed carboxylation of the C–F bond with CO2: a DFT study

Jiao Liu; Wan Nie; Haizhu Yu; Jing Shi

doi:10.1039/D0OB01414A

A mechanistic study on Cu(i) catalyzed carboxylation of the C–F bond with CO₂: a DFT study†

Jiao Liu,^a Wan Nie,^a Haizhu Yu*^b and Jing Shi

*^a

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* Corresponding authors

^a Hefei 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
E-mail: shijing@ustc.edu.cn

^b Department of Chemistry, Center for Atomic Engineering of Advanced Materials, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei, Anhui 230026, China
E-mail: yuhaizhu@ahu.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, syn β-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.

This article is part of the themed collection: Mechanistic, computational & physical organic chemistry in OBC

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Article information

DOI: https://doi.org/10.1039/D0OB01414A
Article type: Paper
Submitted: 11 ஜூலை 2020
Accepted: 19 அக்டோபர் 2020
First published: 22 அக்டோபர் 2020

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Org. Biomol. Chem., 2020,18, 9065-9071

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A mechanistic study on Cu(I) catalyzed carboxylation of the C–F bond with CO₂: a DFT study

J. Liu, W. Nie, H. Yu and J. Shi, Org. Biomol. Chem., 2020, 18, 9065 DOI: 10.1039/D0OB01414A

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Organic & Biomolecular Chemistry