APPLICATION OF THE TERM RELATIVE ENANTIOSELECTIVITY AS USEFUL MEASURE FOR COMPARISON OF CHIRAL CATALYSTS, DEMONSTRATED ON ASYMMETRIC HYDROGENATION OF AMINO-ACID PRECURSORS

被引:48
作者
SELKE, R
FACKLAM, C
FOKEN, H
HELLER, D
机构
[1] Max-Planck Gesellschaft, Arbeitsgruppe Asymmetriche Katalyse an der Universität Rostock, Buchbinderstr. 5-6, 0-2500 Rostock U.K.1 1 In the Institut für Organische Katalyseforschung an der Universität Rostock, e
关键词
D O I
10.1016/S0957-4166(00)86082-6
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The application of the quotient ''relative enantioselectivity'' Q = q/q' in which q and q' are enantiomenc ratios R/S (or S/R) for two comparable cases of asymmetric synthesis experiments is recommended for comparison of two or more catalysts or other variables like solvents, substrates and cofactors. The importance of this term Q lies in the possibility to form and compare values of enantioselectivity over the whole range from 99,9 % ee (R) to 99,9 % ee (S) in a mathematically correct way and is demonstrated on multiple examples of asymmetric hydrogenation of partly new N-acyl-dehydroamino acid derivatives with a couple of catalysts [Rh(Ph-beta-glup)(COD)]BF4 1 and [Rh(Ph-beta-glup-OH)(COD)]BF4 2. Interesting inversions of Q could be discovered for changes of the type of substrate and in dependence of the polarity of solvents.
引用
收藏
页码:369 / 382
页数:14
相关论文
共 50 条
[1]   THE ROLE OF THE PRODUCT IN ASYMMETRIC C-C BOND FORMATION - STOICHIOMETRIC AND CATALYTIC ENANTIOSELECTIVE AUTOINDUCTION [J].
ALBERTS, AH ;
WYNBERG, H .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (18) :7265-7266
[2]  
BREWSTER JH, 1992, CHEM ENG NEWS, V70, P3
[3]   ASYMMETRIC CATALYZES .11. CALCULATION OF ENANTIOSELECTIVITIES IN THE RH-CATALYZED HYDROGENATION OF AMINO-ACID PRECURSORS WITH THE RUCH-UGI MODEL [J].
BRUNNER, H ;
SCHONHAMMER, B ;
SCHONHAMMER, B ;
STEINBERGER, C .
CHEMISCHE BERICHTE-RECUEIL, 1983, 116 (11) :3529-3538
[4]   THE ISOINVERSION PRINCIPLE - A GENERAL-MODEL OF CHEMICAL SELECTIVITY [J].
BUSCHMANN, H ;
SCHARF, HD ;
HOFFMANN, N ;
ESSER, P .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1991, 30 (05) :477-515
[5]  
Buschmann H., 1991, ANGEW CHEM, V103, P480
[6]   ASYMMETRIC-SYNTHESIS OF 2-AMINONORBORNANE-2-CARBOXYLIC ACIDS BY DIELS-ALDER REACTION [J].
CATIVIELA, C ;
LOPEZ, P ;
MAYORAL, JA .
TETRAHEDRON-ASYMMETRY, 1991, 2 (12) :1295-1304
[7]  
Chen C. S., 1989, ANGEW CHEM, V101, P711
[8]   QUANTITATIVE-ANALYSES OF BIOCHEMICAL KINETIC RESOLUTION OF ENANTIOMERS .2. ENZYME-CATALYZED ESTERIFICATIONS IN WATER ORGANIC-SOLVENT BIPHASIC SYSTEMS [J].
CHEN, CS ;
WU, SH ;
GIRDAUKAS, G ;
SIH, CJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (09) :2812-2817
[9]   GENERAL-ASPECTS AND OPTIMIZATION OF ENANTIOSELECTIVE BIOCATALYSIS IN ORGANIC-SOLVENTS - THE USE OF LIPASES [J].
CHEN, CS ;
SIH, CJ .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1989, 28 (06) :695-707
[10]   QUANTITATIVE-ANALYSES OF BIOCHEMICAL KINETIC RESOLUTIONS OF ENANTIOMERS [J].
CHEN, CS ;
FUJIMOTO, Y ;
GIRDAUKAS, G ;
SIH, CJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (25) :7294-7299