从方便易得的原料出发,以钯催化的烯基三氟甲磺酸酯与二苯基膦氧化物的偶联反应为关键步骤,合成了螺[4,4]-1,6-壬二烯骨架的手性双膦配体1.其中,关键中间体5的拆分是通过半制备手性液相色谱实现的,并通过该化合物的X射线单晶衍射分析确定了其中螺碳原子的绝对构型.配体(S)-1的Rh(I)络合物在α-乙酰氨基肉桂酸的氢化中表现出中等的对映选择性(53%ee).配体(S)-1的Cu(I)络合物能以较好的反应活性实现苯乙酮的不对称氢化,产物的对映体过量可以达到67%. Starting from a convenient and accessible starting material, the coupling reaction of palladium catalyzed alkenyl triflate and diphenylphosphine oxide was taken as the key step to synthesize spiro [4,4] -1,6-nonane Alkene framework chiral bisphosphine ligand 1. Among them, the resolution of the key intermediate 5 was achieved by semi-preparative chiral liquid chromatography, and the X-ray single crystal diffraction analysis of the compound confirmed that the spiro carbon atom Absolute configuration The Rh (I) complex of the ligand (S) -1 showed a moderate enantioselectivity (53% ee) in the hydrogenation of α-acetamidocinnamic acid The ligand (S) -1 The Cu (I) complex can react asymmetrically with acetophenone with good reactivity, and the enantiomeric excess of the product can reach 67%.