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Quantitative In Silico Prediction of the Rate of Protodeboronation by a Mechanistic Density Functional Theory-Aided Algorithm.

Published version
Peer-reviewed

Type

Article

Change log

Abstract

Computational reaction prediction has become a ubiquitous task in chemistry due to the potential value accurate predictions can bring to chemists. Boronic acids are widely used in industry; however, understanding how to avoid the protodeboronation side reaction remains a challenge. We have developed an algorithm for in silico prediction of the rate of protodeboronation of boronic acids. A general mechanistic model devised through kinetic studies of protodeboronation was found in the literature and forms the foundation on which the algorithm presented in this work is built. Protodeboronation proceeds through 7 distinct pathways, though for any particular boronic acid, only a subset of mechanistic pathways are active. The rate of each active mechanistic pathway is linearly correlated with its characteristic energy difference, which in turn can be determined using Density Functional Theory. We validated the algorithm using leave-one-out cross-validation on a data set of 50 boronic acids and made a further 50 rate predictions on academically and industrially important boronic acids out of sample. We believe this work will provide great assistance to chemists performing reactions that feature boronic acids, such as Suzuki-Miyaura and Chan-Evans-Lam couplings.

Description

Funder: UCB

Keywords

3404 Medicinal and Biomolecular Chemistry, 34 Chemical Sciences, Bioengineering

Journal Title

J Phys Chem A

Conference Name

Journal ISSN

1089-5639
1520-5215

Volume Title

127

Publisher

American Chemical Society (ACS)
Sponsorship
Engineering and Physical Sciences Research Council (EP/S024220/1)