Projects per year
Abstract
DFT calculations on the full catalytic cycle for manganese catalysed enantioselective hydrogenation of a selection of ketones have been carried out at the PBE0-D3PCM//RI-BP86PCM level. Mn complexes of an enantiomerically pure chiral P,N,N ligand have been found to be most reactive when adopting a facial coordination mode. The use of a new ligand with an ortho-substituted dimethylamino-pyridine motif has been calculated to completely transform the levels of enantioselectivity possible for the hydrogenation of cyclic ketones relative to the first-generation Mn catalysts. In silico evaluation of substrates has been used to identify those likely to be reduced with high enantiomer ratios (er), and others that would exhibit less selectivity; good agreements were then found in experiments. Various cyclic ketones and some acetophenone derivatives were hydrogenated with er's up to 99:1.
Original language | English |
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Article number | e202212479 |
Number of pages | 7 |
Journal | Angewandte Chemie International Edition |
Volume | 62 |
Issue number | 3 |
Early online date | 8 Dec 2022 |
DOIs | |
Publication status | Published - 16 Jan 2023 |
Keywords
- Asymmetric reduction
- Computational design
- Earth abundant metals
- Chirality
- Pincer ligands
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EaSI-CAT - IBioIC Industry Contribution: EaSI-CAT - IBioIC Industry Contribution
Smith, A. D. (PI)
1/08/21 → 30/09/27
Project: Standard
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CRITICAT CDT: Critical Resource Catalysis - CRITICAT
Smith, A. D. (PI), Nolan, S. P. (CoI) & Westwood, N. J. (CoI)
1/05/14 → 31/10/22
Project: Standard
Datasets
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Rational Design of a Facially Coordinating P,N,N Ligand for Manganese-Catalysed Enantioselective Hydrogenation of Cyclic Ketones (dataset)
Oates, C. (Creator), Goodfellow, A. S. (Creator), Buehl, M. (Creator) & Clarke, M. (Creator), University of St Andrews, 14 Dec 2022
DOI: 10.17630/4b784bb5-68a9-4547-b976-e6c037d90c69
Dataset
File