新型手性双膦配体的合成及其催化性能考察

Synthesis of a Novel Chiral Diphosphine Ligand and a Study on Its Catalytic Characters

以苯乙烯为原料,通过Sharpless不对称二羟基化反应合成高对映体纯的苯基乙二醇,经环化、亲核开环和取代反应转化为手性碳膦-氧膦型双膦配体.后者与[Rh(COD)Cl]2及NH4PF6作用生成手性膦-铑阳离子催化剂.在α-脱氢氨基酸衍生物的不对称氢化反应中,化学转化率为100%,对映选择性最高达到77%ee.

The high enantiomeric pure phenylglycol was synthesized from styrene by sharpless asymmetric dihydroxylation. The product was converted to chiral phosphine-phosphinite ligand by cyclization, nucleophilic ring-opening and substitution respectively. asymmetric hydrogenation of The ligand reacted with [ Rh （COD）C;] 2and NH4PF6 to form cation catalyst. The α-dehydroamino acid derivatives have been accomplished in the presence of catalyst in 100% chemical conversion, and the entioselectivities are up to 77% ee.