Kinetic isotope effect evidence for a concerted hydrogen transfer mechanism in transfer Hydrogenations catalyzed by [p-(Me2CH)C6H4Me]Ru-(NHCHPhCHPhNSO2C6H4-p-CH3)

被引：151

作者：

Casey, CP ^{[1
]}

Johnson, JB ^{[1
]}

机构：

[1] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 68卷 / 05期

关键词：

D O I：

10.1021/jo0205457

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The isotope effects in the reaction of [p-(Me2CH)C6H4Me]Ru(NHCHPhCHPhNSO2C6H4-p-CH3) (1) with isopropyl alcohol were 1.79 for transfer of hydrogen from OH to N and 2.86 for transfer from CH to Ru. The isotope effect for transfer of deuterium from doubly labeled material (k(CHOH)/k(CDOD) = 4.88) was within experimental error of the product of the two individual isotope effects. These isotope effects provide convincing evidence for a mechanism involving concurrent transfer of hydrogen from oxygen to nitrogen and from carbon to ruthenium.

引用

页码：1998 / 2001

页数：4

共 19 条

[1] (CYCLOPENTADIENONE)RUTHENIUM CARBONYL-COMPLEXES - A NEW CLASS OF HOMOGENEOUS HYDROGENATION CATALYSTS
BLUM, Y
CZARKIE, D
RAHAMIM, Y
SHVO, Y
[J]. ORGANOMETALLICS, 1985, 4 (08) : 1459 - 1461
[2] Hydrogen transfer to carbonyls and imines from a hydroxycyclopentadienyl ruthenium hydride: Evidence for concerted hydride and proton transfer
Casey, CP
Singer, SW
Powell, DR
Hayashi, RK
Kavana, M
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (06) : 1090 - 1100
[3] Espenson JH, 1995, Chemical kinetics and reaction mechanisms
[4] Fehring V, 1998, ANGEW CHEM INT EDIT, V37, P1827, DOI 10.1002/(SICI)1521-3773(19980803)37:13/14<1827::AID-ANIE1827>3.0.CO
[5] 2-C
[6] The catalyst precursor, catalyst, and intermediate in the Ru-II-promoted asymmetric hydrogen transfer between alcohols and ketones
Haack, KJ
Hashiguchi, S
Fujii, A
Ikariya, T
Noyori, R
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1997, 36 (03): : 285 - 288
[7] INTEGRATED RATE LAWS FOR REVERSIBLE-REACTIONS
KING, EL
[J]. INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1982, 14 (11) : 1285 - 1286
[8] GENERAL RATE EQUATION FOR REACTIONS GOVERNED BY A SINGLE RELAXATION-TIME
KING, EL
[J]. JOURNAL OF CHEMICAL EDUCATION, 1979, 56 (09) : 580 - 582
[9] The half-sandwich hydride and 16-electron complexes of rhodium and iridium containing (1S,2S)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine:: Relevant to the asymmetric transfer hydrogenation
Mashima, K
Abe, T
Tani, K
[J]. CHEMISTRY LETTERS, 1998, (12) : 1201 - 1202
[10] Asymmetric transfer hydrogenation of ketonic substrates catalyzed by (η5-C5Me5)MCl complexes (M = Rh and Ir) of (1S,2S)-N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine
Mashima, K
Abe, T
Tani, K
[J]. CHEMISTRY LETTERS, 1998, (12) : 1199 - 1200

← 1 2 →