Hu Aiguo, Ngo Helen L, Lin Wenbin
Department of Chemistry, CB#3290, University of North Carolina, Chapel Hill, North Carolina 27599, USA.
Org Lett. 2004 Aug 19;6(17):2937-40. doi: 10.1021/ol048993j.
A family of tunable precatalysts Ru(4,4'-BINAP)(chiral diamine)Cl2 was synthesized and used for highly enantioselective hydrogenation of aromatic ketones. This result differs from previous chiral diphosphines that rely on the bis(xylyl)phosphino groups to control enantioselectivity. An X-ray structural study reveals that the bulky substituents on the 4,4'-positions of BINAP can effectively create a suitable chiral pocket in the transition state and thus provide a new mechanism for the enantiocontrol in such a remarkable asymmetric catalytic process.
合成了一系列可调节的预催化剂Ru(4,4'-联萘二苯基膦)(手性二胺)Cl2，并将其用于芳香酮的高对映选择性氢化反应。该结果与之前依赖双(二甲苯基)膦基来控制对映选择性的手性二膦不同。X射线结构研究表明，联萘二苯基膦4,4'-位上的庞大取代基能够有效地在过渡态中形成合适的手性口袋，从而为这一显著的不对称催化过程中的对映体控制提供了一种新机制。
