Rational Design of a Facially Coordinating <i>P,N,N</i> Ligand for Manganese?Catalysed Enantioselective Hydrogenation of Cyclic Ketones

DFT calculations on the full catalytic cycle for manganese catalysed enantioselective hydrogenation of a selection ketones have been carried out at PBE0-D3PCM//RI-BP86PCM level. Mn complexes an enantiomerically pure chiral P,N,N ligand found to be most reactive when adopting facial coordination mode. The use new with ortho-substituted dimethylamino-pyridine motif has calculated completely transform levels enantioselectivity possible cyclic relative first-generation catalysts. In silico evaluation substrates used identify those likely reduced high enantiomer ratios (er), and others that would exhibit less selectivity; good agreements were then in experiments. Various some acetophenone derivatives hydrogenated er's up 99 : 1.