MECHANISM AND STEREOSELECTIVITY OF ASYMMETRIC HYDROGENATION
MECHANISM AND STEREOSELECTIVITY OF ASYMMETRIC HYDROGENATION
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DOI：
10.1126/science.217.4558.401
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发表时间：
1982-01-01
期刊：
影响因子：
56.9
通讯作者：
HALPERN, J
中科院分区：
文献类型：
--
作者：
HALPERN, J
含手性膦配体的铑配合物催化α-氨基丙烯酸衍生物等烯烃底物的加氢反应，生成具有非常高光学产率的手性产品。对这些反应机理的阐明导致了这样的结论：立体选择性不是由底物与手性催化剂的优先初始结合决定的，而是由催化剂-底物加合物的次要非对映异构体对应于较不有利的结合模式的高得多的反应活性决定的。
Rhodium complexes containing chiral phosphine ligands catalyze the hydrogenation of olefinic substrates such as α-aminoacrylic acid derivatives, producing chiral products with very high optical yields. Elucidation of the mechanisms of such reactions leads to the conclusion that the stereoselection is dictated not by the preferred initial binding of the substrate to the chiral catalyst, but rather by the much higher reactivity of the minor diastereomer of the catalyst-substrate adduct corresponding to the less favored binding mode.