Synthesis of a New Rigid Bicyclic AMPP Ligand (TIAMPP) and Application in Asymmetric Hydrogenation

The new rigid bicyclic AMPP（（S）-TIAMPP） has been synthesized from the corresponding Ticol and Ph2PCI. The application of （S）-TIAMPP in Rh-catalyzed asymmetric hydrogenation of α-dehydroamino acids derivatives has been examined. Up to 93% ee was obtained.

六元N-杂环配体TIAMPP的合成及其在不对称催化加氢中的应用

在三乙胺的作用下,利用(S)-3-羟甲基-1,2,3,4-四氢异喹啉((S)-TicOL)和Ph2PC l缩合,得到六元N-杂环配体(S)-TIAMPP.研究了(S)-TIAMPP与Rh(I)形成的手性催化剂[Rh((S)-TIAMPP)(COD)]BF4在脱氢氨基酸的衍生物中不对称催化加氢的对映选择性和适应性,以及该催化剂对N-苯甲酰基脱氢肉桂酸甲酯加氢过程中温度、压力、反应溶剂、底物与催化剂比例(S/C)对光学收率的影响.结果表明,在S/C=100,15℃,1.0MPa的甲醇溶液中,反应24 h,[Rh((S)-TIAMPP)(COD)]BF4对N-苯甲酰基脱氢肉桂酸甲酯加氢的光学收率可达到96%.