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(-)-3-CH3-DIOP的制备及其膦-铑(Ⅰ)络合物在不对称氢化反应中的应用
THE PREPARATION OF (-)-3-CH3-DIOP AND APPLICATION OF ITS PHOSPHINE-RHODIUM COMPLEX IN CATALYTIC ASYMETRIC HYDROGENATION
【摘要】 用钠-钾合金代替金属锂分解三间甲苯膦生成(3-CH3C6H4)2PK,后者与二磺酸酯(V)反应形成(-)-3-CH3-DIOP,粗产品经用醇、醚处理得到(-)-3-CH3-DJOP,产率为78%。Rh(I)-(-)-3-CH3-DIOP催化剂对Ia和Ic的氢化具有较高的立体选择性,旋光产率分别为91和92%。对Ib和Id的氢化仅有中等的立体选择性,旋光产率分别为80%和70%。
【Abstract】 Tris(3-methylphenyl)phosphine was cleaved with sodium-potassium alloy in place of metallic lithium to give (3-CH3C6H4)2PK which reacts with ditosylate(Ⅴ) to form (-)-3-CH3-DIOP. The treatment of the crude product with alcohol and ether (-)-3-CH3-DIOP is obtained in 78% yield.Rh(Ⅰ)-(-)-3-CH3-DIOP catalyst possesses a higher stereoselectivity for the hydrogenation of Ia and Ic, and the optical yield is 91 and 92 per cent, respectively, for the hydrogenation of Ib and Id possesses only a moderate steroselectivity, and the optical yield is 80 and 70 per cent respectively.
- 【文献出处】 天津大学学报 ,Journal of Tianjin University , 编辑部邮箱 ,1985年02期
- 【被引频次】2
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