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Asymmetric hydrogenation of an α-unsaturated carboxylic acid catalyzed by intact chiral transition metal carbonyl clusters - diastereomeric control of enantioselectivity.
Dalton Transactions ( IF 3.5 ) Pub Date : 2020/02/27 , DOI: 10.1039/c9dt04799a Ahmed F Abdel-Magied 1 , Yusuf Theibich 1 , Amrendra K Singh 1 , Ahibur Rahaman 1 , Isa Doverbratt 2 , Arun K Raha 1 , Matti Haukka 3 , Michael G Richmond 4 , Ebbe Nordlander 1
Dalton Transactions ( IF 3.5 ) Pub Date : 2020/02/27 , DOI: 10.1039/c9dt04799a Ahmed F Abdel-Magied 1 , Yusuf Theibich 1 , Amrendra K Singh 1 , Ahibur Rahaman 1 , Isa Doverbratt 2 , Arun K Raha 1 , Matti Haukka 3 , Michael G Richmond 4 , Ebbe Nordlander 1
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Twenty clusters of the general formula [(μ-H)2Ru3(μ3-S)(CO)7(μ-P-P*)] (P-P* = chiral diphosphine of the ferrocene-based Walphos or Josiphos families) have been synthesised and characterised. The clusters have been tested as catalysts for asymmetric hydrogenation of tiglic acid [trans-2-methyl-2-butenoic acid]. The observed enantioselectivities and conversion rates strongly support catalysis by intact Ru3 clusters. A catalytic mechanism involving an active Ru3 catalyst generated by CO loss from [(μ-H)2Ru3(μ3-S)(CO)7(μ-P-P*)] has been investigated by DFT calculations.
中文翻译：
完整手性过渡金属羰基簇催化的α-不饱和羧酸的不对称氢化-对映体选择性的非对映体控制。
合成并表征了二十个通式为[（μ-H）2Ru3（μ3-S）（CO）7（μ-PP*）]的簇（PP * =二茂铁基Walphos或Josiphos家族的手性二膦） 。已经测试了该团簇作为对tig酸[反式-2-甲基-2-丁烯酸]不对称氢化的催化剂。观察到的对映选择性和转化率强烈支持完整的Ru3团簇的催化作用。通过DFT计算研究了由[（μ-H）2Ru3（μ3-S）（CO）7（μ-PP*）]的CO损失产生的活性Ru3催化剂的催化机理。
更新日期：2020-04-08
中文翻译：
完整手性过渡金属羰基簇催化的α-不饱和羧酸的不对称氢化-对映体选择性的非对映体控制。
合成并表征了二十个通式为[（μ-H）2Ru3（μ3-S）（CO）7（μ-PP*）]的簇（PP * =二茂铁基Walphos或Josiphos家族的手性二膦） 。已经测试了该团簇作为对tig酸[反式-2-甲基-2-丁烯酸]不对称氢化的催化剂。观察到的对映选择性和转化率强烈支持完整的Ru3团簇的催化作用。通过DFT计算研究了由[（μ-H）2Ru3（μ3-S）（CO）7（μ-PP*）]的CO损失产生的活性Ru3催化剂的催化机理。
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