Rational design of a facially coordinating P,N,N ligand for manganese-catalysed enantioselective hydrogenation of cyclic ketones

Conor L. Oates, Alister S. Goodfellow, Michael Bühl*, Matthew L. Clarke*

*Corresponding author for this work

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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 languageEnglish
Article numbere202212479
Number of pages7
JournalAngewandte Chemie International Edition
Volume62
Issue number3
Early online date8 Dec 2022
DOIs
Publication statusPublished - 16 Jan 2023

Keywords

  • Asymmetric reduction
  • Computational design
  • Earth abundant metals
  • Chirality
  • Pincer ligands

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