Oxidation of olefins by palladium(II) Part 17. An asymmetric chlorohydrin synthesis catalyzed by a bimetallic palladium(II) complex

被引:43
作者
El-Qisairi, A [1 ]
Henry, PM [1 ]
机构
[1] Loyola Univ, Dept Chem, Chicago, IL 60626 USA
关键词
palladium(II); catalysis; asymmetric; olefins; chlorohydrins;
D O I
10.1016/S0022-328X(00)00070-X
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Previous studies showed that oxidation of cl-olefins with monometallic catalysts containing chiral diphosphines and diamines gave chlorohydrins with poor to good enantioselectivites (28-82% ee). The present studies demonstrate that bimetallic catalysts containing a beta-triketone and bridging chiral diphosphine and diamines are excellent catalysts for this reaction giving enantioselectivites considerably higher than the monometallic catalysts. Enantioselectivities were more than 50% for most olefins tested. The highest optical purities were 94% ee for propene and 93% ee for allylphenyl ether. A useful feature of this asymmetric synthesis is the fact it is a net air oxidation. (C) 2000 Elsevier Science S.A. All rights reserved.
引用
收藏
页码:50 / 60
页数:11
相关论文
共 20 条
[1]  
AIKEN RA, 1992, ASYMMETRIC SYNTHESIS, P220
[2]   CHIRAL SULFONATED PHOSPHINES - SYNTHESES AND USE AS LIGANDS IN ASYMMETRIC HYDROGENATION USING AN AQUEOUS ORGANIC 2-PHASE SOLVENT SYSTEM [J].
AMRANI, Y ;
LECOMTE, L ;
SINOU, D ;
BAKOS, J ;
TOTH, I ;
HEIL, B .
ORGANOMETALLICS, 1989, 8 (02) :542-547
[3]  
BACKVALL JE, 1979, J AM CHEM SOC, V101, P2411
[4]   RHODIUM(I) SULFONATED-BDPP CATALYZED ASYMMETRIC HYDROGENATION OF IMINES IN AQUEOUS ORGANIC 2-PHASE SOLVENT SYSTEMS [J].
BAKOS, J ;
OROSZ, A ;
HEIL, B ;
LAGHMARI, M ;
LHOSTE, P ;
SINOU, D .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1991, (23) :1684-1685
[5]   ORGANIC REACTIONS IN AQUEOUS SOLUTION AT ROOM TEMPERATURE .3. INFLUENCE OF PH ON SELF-CONDENSATION OF DIACETYLACETONE - CONSTITUTION OF COLLIES NAPHTHALENE DERIVATIVE [J].
BETHELL, JR ;
MAITLAND, P .
JOURNAL OF THE CHEMICAL SOCIETY, 1962, (SEP) :3751-&
[6]  
BOVEY FA, 1988, NUCL MAGNETIC RESONA, P617
[7]  
DRAGO RS, PHYSICAL METHODS CHE, P222
[8]   A new palladium(II)-catalyzed asymmetric chlorohydrin synthesis [J].
El-Qisairi, A ;
Hamed, O ;
Henry, PM .
JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (09) :2790-2791
[9]  
ELQISAIRI A, UNPUB
[10]   OXIDATION OF OLEFINS BY PALLADIUM(II) .14. PRODUCT DISTRIBUTION AND KINETICS OF THE OXIDATION OF ETHENE BY PDCL3(PYRIDINE)(-) IN AQUEOUS-SOLUTION IN THE PRESENCE AND ABSENCE OF CUCL2 - A MODIFIED WACKER CATALYST WITH ALTERED REACTIVITY [J].
FRANCIS, JW ;
HENRY, PM .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1995, 99 (02) :77-86