Rational design of a facially coordinating P,N,N ligand for manganese-catalysed enantioselective hydrogenation of cyclic ketones
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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.
Oates , C L , Goodfellow , A S , Bühl , M & Clarke , M L 2023 , ' Rational design of a facially coordinating P,N,N ligand for manganese-catalysed enantioselective hydrogenation of cyclic ketones ' , Angewandte Chemie International Edition , vol. 62 , no. 3 , e202212479 . https://doi.org/10.1002/anie.202212479
Angewandte Chemie International Edition
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DescriptionFunding: Authors would like to thank the University of St Andrews, combined with the EPSRC Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT) for financial support [PhD studentship to CO; Grant code: EP/L016419/1], and the EaSI-CAT programme PhD studentship to AG].
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