EaStCHEM School of Chemistry, University of St Andrews, Purdie Building, North Haugh, St Andrews, KY16 9ST, UK.
Angew Chem Int Ed Engl. 2023 Jan 16;62(3):e202212479. doi: 10.1002/anie.202212479. Epub 2022 Dec 8.
DFT calculations on the full catalytic cycle for manganese catalysed enantioselective hydrogenation of a selection of ketones have been carried out at the PBE0-D3 //RI-BP86 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.
采用 PBE0-D3 // RI-BP86 方法对一系列酮的锰催化对映选择性氢化的完整催化循环进行了密度泛函理论（DFT）计算。当采用面配位模式时，手性 P,N,N 配体的锰络合物的反应活性最高。计算表明，使用具有邻位取代的二甲基氨基吡啶基序的新型配体，可使环状酮氢化的对映选择性水平相对于第一代 Mn 催化剂完全改变。通过计算对底物进行了计算机模拟评估，以确定那些可能具有高对映体过量（er）的还原产物，以及那些可能选择性较低的还原产物；然后在实验中发现了很好的一致性。各种环状酮和一些苯乙酮衍生物的氢化反应具有高达 99：1 的 er。
