Selectivity from a kinetic point of view: nonlinear behavior of logarithmic product ratios as a function of the reciprocal temperature

被引：26

作者：

Heller, D

Buschmann, H

机构：

[1] Univ Rostock, Inst Organ Katalyseforsch, D-18055 Rostock, Germany

[2] Grunenthal GmbH, Forschungszentrum, D-52078 Aachen, Germany

来源：

TOPICS IN CATALYSIS | 1998年 / 5卷 / 1-4期

关键词：

nonlinear temperature behavior; Eyring plot; modified Eyring plot; selectivity; selection process; enantioselectivity; selection level; isoinversion principle; isoinversion temperature; inversion temperature; kinetics; catalysis; asymmetric hydrogenation; dihydroxylation; cocyclization;

D O I：

10.1023/A:1019185532627

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

The influence of the temperature on selectivity is described under special consideration of nonlinearities in the corresponding modified Eyring plots. Reasons for the experimentally well-known behavior are discussed. Furthermore, the conditions for nonlinear temperature behavior are quantified and a concept is described which allows the determination of the temperature dependence of a single reaction pathway in a selection process.

引用

页码：159 / 176

页数：18

共 87 条

[41] ASYMMETRIC HYDROGENATION USING READILY PREPARED CHIRAL SUGAR DIPHOSPHINITERHODIUM COMPLEXES
JACKSON, R
THOMPSON, DJ
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1978, 159 (04) : C29 - C31
[42] CATALYST-SUBSTRATE COMPLEXES OF CHIRAL 7-MEMBERED RING CHELATES OF RHODIUM(I)-BIS(PHOSPHINITES)
KADYROV, R
FREIER, T
HELLER, D
MICHALIK, M
SELKE, R
[J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1995, (17) : 1745 - 1746
[43] Kagan H.B., 2007, TOPICS STEREOCHEMIST, V18, P249, DOI 10.1002/9780470147276.ch4
[44] KAGAN HB, 1995, RECL TRAV CHIM PAY B, V114, P203
[45] Ab initio studies of rhodium(I)-N-alkenylamide complexes with cis- and trans-coordinating phosphines: Relevance for the mechanism of catalytic asymmetric hydrogenation of prochiral dehydroamino acids
Kless, A
Borner, A
Heller, D
Selke, R
[J]. ORGANOMETALLICS, 1997, 16 (10) : 2096 - 2100
[46] CATALYTIC ASYMMETRIC DIHYDROXYLATION
KOLB, HC
VANNIEUWENHZE, MS
SHARPLESS, KB
[J]. CHEMICAL REVIEWS, 1994, 94 (08) : 2483 - 2547
[47] TOWARD AN UNDERSTANDING OF THE HIGH ENANTIOSELECTIVITY IN THE OSMIUM-CATALYZED ASYMMETRIC DIHYDROXYLATION (AD) .1. KINETICS
KOLB, HC
ANDERSSON, PG
SHARPLESS, KB
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (04) : 1278 - 1291
[48] KRAUSE HW, 1989, NEW J CHEM, V13, P615
[49] KRAUSE HW, 1995, J MOL CATAL A-CHEM, V104, P145
[50] ASYMMETRIC HYDROGENATION OF METHYL-(Z)-ALPHA-ACETAMIDOCINNAMATE CATALYZED BY (1,2-BIS((PHENYL-ORTHO-ANISOYL)PHOSPHINO)ETHANE)RHODIUM(I) - KINETICS, MECHANISM, AND ORIGIN OF ENANTIOSELECTION
LANDIS, CR
HALPERN, J
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (06) : 1746 - 1754

← 1 2 3 4 5 6 7 8 9 →