A computational investigation into the Cu-catalysed borylation of α,β-unsaturated compounds
Jasmine Catlow , Ben M. Partridge and J. Grant Hill Department of Chemistry, University of Sheffield, UK
Boronic esters are versatile building blocks for use in pharmaceutical synthesis, as they react under mild, functional group tolerant conditions. 1 This work develops a combined semi-empirical and DFT workflow to investigate the origins of stereoselectivity for a Cu-catalysed boronic ester synthesis developed by the Partridge group. 2 The main challenges of this work arise from modelling large organometallic complexes with two metal centres and chiral ligands. A simplified mechanism was modelled to determine the general mechanistic pathway, 3 followed by benchmarking of exchange-correlation functionals and basis sets. The full reaction was then modelled, and semi-empirical methods such as xTB 4 and CREST 5 were used to find low energy conformers and pre-optimise structures, before using DFT methods to obtain final geometries and energies. This poster will provide an overview of the benchmarking data, a detailed workflow, and a proposed mechanism with energy profile diagrams for the mechanisms modelled. References 1. A. T. K. Koshvandi, M. M. Heravi, and T. Momeni, Appl. Organometal. Chem ., 2018 , 32, 3, 4210 2. G. Rodgers,E. J. Wilson,C. C. Robertson,D. J. Cox, B. M. Partridge, Advanced Synthesis and Catalysis , 2021 , 363, 9, 2392–2395 3. L. Dang, Z. Lin and T. B. Marder, Organometallics , 2008 , 27, 17, 4443–4454 4. C. Bannwarth , S. Ehlert, and S. Grimme , J. Chem. Theory Comput ., 2019 , 15, 3, 1652–1671 5. S. Grimme, J. Chem. Theory Comput ., 2019 , 15, 5, 2847−2862
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© The Author(s), 2023
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