钯-手性膦催化降冰片烯的不对称氢酯基化反应  

ASYMMETRIC HYDROESTERIFICATION OF NORBORNENE CATALYZED BYCHIRAL NONCHELATE BIPHOSPHINEPALLADIUM COMPLEXES

作　　者：周宏英[1] 侯经国[1] 陈静[1] 吕士杰[1] 傅宏祥[1] 汪汉卿[1] 

机构地区：[1]中国科学院兰州化学物理研究所

出　　处：《催化学报》1998年第3期247-250,共4页

基　　金：国家自然科学基金;中国石化总公司石油化工科学研究院资助项目

摘　　要：首次用Ｐｄ（ＯＡｃ）２－１，４∶３，６－双脱水－２，５－二（二苯基膦）－Ｌ－艾杜糖醇（ＤＤＰＰＩ）－ｐ－ＴｓＯＨ催化体系对降冰片烯进行了不对称氢酯基化反应，获得了较好的结果．考察了手性膦配体的结构以及磷原子与钯原子的摩尔比对反应的影响，发现在一个磷原子配位一个钯原子时，获得了较高的光学产率．同时考察了反应温度、反应压力及溶剂对降冰片烯不对称氢酯基化反应的影响，发现在１２０℃，５．０ＭＰａ，ｎ（Ｐ）／ｎ（Ｐｄ）＝１时，化学产率可达７１．６％，光学产率可达９２．２％．Hydroesterification and hydroformylation reactions of olefins catalyzed by metal complex are extensively investigated in homogeneous catalytic process. The asymmetric hydroesterification of norbornene using palladium acetate, 1,4∶3,6dianhydro2,5bis(diphenylphosphino)Liditol (DDPPI) and ptoluenesulfonic acid (pTsOH) catalytic system under mild reaction conditions was studied. The nature of DDPPI plays an important role in asymmetric hydroesterification of norbornene. Experimental results show that DDPPI is an effective chiral ligand for hydroesterification of norbornene. The higher optical yield was obtained when the P/Pd molar ratio was kept at 1∶1. Effect of the reaction temperature, pressure, and solvent on asymmetric hydroesterification of norbonene has also been investigated with this catalyst system. Optical yield up to 922% and good chemical yield 716% are obtained under 50 MPa, 120℃, and n(P)/n(Pd)=1.

关 键 词：降冰片烯 不对称 氢酯基化 手性膦 催化剂 钯 

分 类 号：O643.36[理学—物理化学] O624.12[理学—化学]