Ligand-modulated palladium oxidation catalysis:: Mechanistic insights into aerobic alcohol oxidation with the Pd(OAc)2/pyridine catalyst system

被引：187

作者：

Steinhoff, BA ^{[1
]}

Stahl, SS ^{[1
]}

机构：

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

来源：

ORGANIC LETTERS | 2002年 / 4卷 / 23期

关键词：

D O I：

10.1021/ol026988e

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] Pd(OAc)(2):pyridine (1:4) is an efficient catalyst system for the oxidation of alcohols with molecular oxygen. A mechanistic study of this reaction reveals that pyridine promotes the aerobic oxidation. of palladium(0) but inhibits the oxidation of alcohol by palladium(II). Kinetic results reveal that turnover-limiting substrate oxidation consists of (i) formation of a palladium(II)-alkoxide, (ii) pyridine dissociation, and (iii) beta-hydride elimination. These results provide a framework for the design and/or screening of more effective aerobic oxidation catalysts.

引用

页码：4179 / 4181

页数：3

共 30 条

[1] COMPETITIVE UNCATALYZED GEOMETRICAL ISOMERIZATION AND BETA-HYDRIDE ELIMINATION OF ALKYL COMPLEXES OF PLATINUM(II)
ALIBRANDI, G
CUSUMANO, M
MINNITI, D
SCOLARO, LM
ROMEO, R
[J]. INORGANIC CHEMISTRY, 1989, 28 (02) : 342 - 347
[2] HOMOGENEOUS CATALYTIC-OXIDATION OF SECONDARY ALCOHOLS TO KETONES BY MOLECULAR-OXYGEN UNDER MILD CONDITIONS
BLACKBURN, TF
SCHWARTZ, J
[J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1977, (05) : 157 - 158
[3] Production of hydrogen peroxide from oxygen and alcohols, catalyzed by palladium complexes
Bortolo, R
Bianchi, D
D'Aloisio, R
Querci, C
Ricci, M
[J]. JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2000, 153 (1-2) : 25 - 29
[4] BETA-HYDRIDE ELIMINATION FROM METHOXO VS ETHYL LIGANDS - THERMOLYSIS OF (DPPE)PT(OCH3)2, (DPPE)PT(CH2CH3)(OCH3) AND (DPPE)PT(CH2CH3)2
BRYNDZA, HE
CALABRESE, JC
MARSI, M
ROE, DC
TAM, W
BERCAW, JE
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (16) : 4805 - 4813
[5] The palladiuim-catalyzed oxidative kinetic resolution of secondary alcohols with molecular oxygen
Ferreira, EM
Stoltz, BM
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (31) : 7725 - 7726
[6] Fix SR, 2002, ANGEW CHEM INT EDIT, V41, P164, DOI 10.1002/1521-3773(20020104)41:1<164::AID-ANIE164>3.0.CO
[7] 2-B
[8] Mechanistic studies of the cycloisomerization of dimethyl diallylmalonate catalyzed by a cationic palladium phenanthroline complex
Goj, LA
Widenhoefer, RA
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (45) : 11133 - 11147
[9] FORMATION OF ALPHA,BETA-UNSATURATED CARBONYL-COMPOUNDS BY PALLADIUM-CATALYZED OXIDATION OF ALLYLIC ALCOHOLS
GOMEZBENGOA, E
NOHEDA, P
ECHAVARREN, AM
[J]. TETRAHEDRON LETTERS, 1994, 35 (38) : 7097 - 7098
[10] Hallman K, 2001, ADV SYNTH CATAL, V343, P260, DOI 10.1002/1615-4169(20010330)343:3<260::AID-ADSC260>3.3.CO

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