Issue 15, 2022

Computational mechanism investigation of bismuth (BiIII/BiV) redox-catalyzed fluorination of arylboronic esters

Abstract

Recently, the Cornella group has achieved bismuth redox-catalyzed fluorination of arylboronic esters by using heavier main group elements to simulate the transition metal catalytic cycle method. Despite the great efforts made by the experimental group, details regarding the mechanism remained unclear. In this work, detailed DFT calculations were carried out to elucidate the principal features of this transformation. The results reveal the following: (1) the entire conversion is thermodynamically favorable, with a free energy decrease of 124.4 kcal mol−1; (2) the activator KF not only is beneficial to assisting the dissociation of BF3 on the bismuth catalyst to facilitate transmetallization, but may also be a potential promoter of BF4 dissociation in the reductive elimination step; (3) the sulfone fragment is favorable for reductive elimination; and (4) pyridyl fluoride may be responsible for the smooth progress of the oxidative addition.

Graphical abstract: Computational mechanism investigation of bismuth (BiIII/BiV) redox-catalyzed fluorination of arylboronic esters

Supplementary files

Article information

Article type
Paper
Submitted
24 Mar 2022
Accepted
18 May 2022
First published
19 May 2022

Catal. Sci. Technol., 2022,12, 4688-4697

Computational mechanism investigation of bismuth (BiIII/BiV) redox-catalyzed fluorination of arylboronic esters

F. Jia, J. Luo and B. Zhang, Catal. Sci. Technol., 2022, 12, 4688 DOI: 10.1039/D2CY00565D

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