Influence of a remote hydroxy group in the ligand on the reactivity of a chiral hydrogenation catalyst

被引:30
作者
Heller, D
Holz, J
Borns, S
Spannenberg, A
Kempe, R
Schmidt, U
Borner, A
机构
[1] UNIV ROSTOCK,MAX PLANCK GESELL FORDERUNG WISSENSCH,ARBEITSGRP ASYMMETR KATALYSE,D-18055 ROSTOCK,GERMANY
[2] UNIV ROSTOCK,INST ORGAN KATALYSEFORSCH,D-18055 ROSTOCK,GERMANY
关键词
D O I
10.1016/S0957-4166(96)00522-8
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A kinetic study concerning the asymmetric hydrogenation of prochiral olefins by chiral diphosphine rhodium cyclooctadiene complexes based on HO-DIOPs is presented. The investigations have been carried out in order to show the influence of a remote hydroxy group on the rate of the reaction. Since in methanol under standard conditions the reactivities of all catalysts elaborated were too high, the hydrogenation experiments have been performed under reduced hydrogen pressure affording the desired reduction in rate. To avoid the induction period caused by the hydrogenation of the cyclooctadiene all precatalysts were prehydrogenated before the prochiral substrates were added. For comparison analogous Rh-DIOP complexes with the same structural framework, but without the hydroxy group in the backbone have been proven. For all hydroxy catalysts investigated a lower reactivity has been observed compared to the parent complexes, although a direct interaction between HO-group and reaction center can be presumably excluded. This assumption is supported by the X-ray structural analysis of one of the complexes which shows the remote position of the HO-group related to the metal center. (C) 1997 Elsevier Science Ltd.
引用
收藏
页码:213 / 222
页数:10
相关论文
共 40 条
[1]   CHIRAL 1,2-DIPHOSPHINE LIGANDS - SYNTHESIS AND APPLICATION TO RHODIUM-CATALYZED ASYMMETRIC HYDROGENATIONS [J].
AMMA, JP ;
STILLE, JK .
JOURNAL OF ORGANIC CHEMISTRY, 1982, 47 (03) :468-473
[2]   RHODIUM COMPLEXES OF 1,4-BIS(DIPHENYLPHOSPHINO)BUTANE - CRYSTAL AND MOLECULAR-STRUCTURES OF [RH(DPPB)2]BF4.C4H10O AND [RH(COD)(DPPB)]BF4 [J].
ANDERSON, MP ;
PIGNOLET, LH .
INORGANIC CHEMISTRY, 1981, 20 (12) :4101-4107
[3]   CHIRAL SULFONATED PHOSPHINES .9. ROLE OF WATER IN THE HYDROGENATION OF DEHYDRO AMINO-ACIDS [J].
BAKOS, J ;
KARAIVANOV, R ;
LAGHMARI, M ;
SINOU, D .
ORGANOMETALLICS, 1994, 13 (08) :2951-2956
[4]  
Berrisford D.J., 1995, ANGEW CHEM, V107, P1159
[5]   LIGAND-ACCELERATED CATALYSIS [J].
BERRISFORD, DJ ;
BOLM, C ;
SHARPLESS, KB .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1995, 34 (10) :1059-1070
[6]   INTERCONVERSION OF DIASTEREOMERIC COMPLEXES INVOLVED IN RH(I)-CATALYZED ASYMMETRIC HYDROGENATION - A(P-31,P-31) EXSY NMR-STUDY [J].
BIRCHER, H ;
BENDER, BR ;
VONPHILIPSBORN, W .
MAGNETIC RESONANCE IN CHEMISTRY, 1993, 31 (03) :293-298
[7]   SYNTHESIS OF AN OPTICALLY-ACTIVE HYDROXY DIPHOSPHINE, A NEW LIGAND FOR ASYMMETRIC CATALYSIS [J].
BORNER, A ;
HOLZ, J ;
KLESS, A ;
HELLER, D ;
BERENS, U .
TETRAHEDRON LETTERS, 1994, 35 (33) :6071-6074
[8]   BETA-ALKOXYALKYLPHOSPHANES AND BETA-HYDROXYALKYLPHOSPHANES AS LIGANDS IN THE STEREOSELECTIVE HYDROGENATION - A COMPARISON [J].
BORNER, A ;
KLESS, A ;
KEMPE, R ;
HELLER, D ;
HOLZ, J ;
BAUMANN, W .
CHEMISCHE BERICHTE, 1995, 128 (08) :767-773
[9]   SYNTHESIS AND CATALYTIC PROPERTIES OF AN ACYCLIC ANALOG OF HYDROXY NORPHOS [J].
BORNER, A ;
WARD, J ;
RUTH, W ;
HOLZ, J ;
KLESS, A ;
HELLER, D ;
KAGAN, HB .
TETRAHEDRON, 1994, 50 (35) :10419-10430
[10]   THE CATALYTIC RESTING STATE OF ASYMMETRIC HOMOGENEOUS HYDROGENATION - EXCHANGE PROCESSES DELINEATED BY NUCLEAR-MAGNETIC-RESONANCE SATURATION-TRANSFER (DANTE) TECHNIQUES [J].
BROWN, JM ;
CHALONER, PA ;
MORRIS, GA .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1987, (11) :1583-1588