Rational Design of a Facially CoordinatingP,N,NLigand for Manganese‐Catalysed Enantioselective Hydrogenation of Cyclic Ketones

Abstract

AbstractDFT 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‐BP86PCMlevel. Mn complexes of an enantiomerically pure chiralP,N,Nligand have been found to be most reactive when adopting a facial coordination mode. The use of a new ligand with anortho‐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 silicoevaluation 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 wither'sup to 99 : 1.