Mechanistic investigation of the gold-catalyzed aerobic oxidation of alcohols

被引：85

作者：

Fristrup, Peter ^{[1
]}

Johansen, Louise Bahn ^{[1
]}

Christensen, Claus Hviid ^{[1
]}

机构：

[1] Tech Univ Denmark, Ctr Sustainable & Green Chem, DK-2800 Lyngby, Denmark

来源：

CATALYSIS LETTERS | 2008年 / 120卷 / 3-4期

关键词：

heterogeneous catalysis; oxidations; gold; mechanism; Hammett;

D O I：

10.1007/s10562-007-9301-8

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The mechanism for the gold-catalyzed aerobic oxidation of alcohols was studied using a series of para-substituted benzyl alcohols (Hammett methodology). The competition experiments clearly show that the rate-determining step of the reaction involves the generation of a partial positive charge in the benzylic position (i.e. hydride abstraction). This was further substantiated by the determination of a significant kinetic isotope effect (k(H)/k(D) = 1.41), when employing an alcohol substrate deuterated in this position.

引用

页码：184 / 190

页数：7

共 38 条

[1] Unique gold chemoselectivity for the aerobic oxidation of allylic alcohols [J].

Abad, Alberto ;

Almela, Carles ;

Corma, Avelino ;

Garcia, Hermenegildo .

CHEMICAL COMMUNICATIONS, 2006, (30) :3178-3180

[2] Selective liquid phase oxidation using gold catalysts [J].

Bianchi, C ;

Porta, F ;

Prati, L ;

Rossi, M .

TOPICS IN CATALYSIS, 2000, 13 (03) :231-236

[3] Application of gold catalysts to selective liquid phase oxidation [J].

Biella, S ;

Castiglioni, GL ;

Fumagalli, C ;

Prati, L ;

Rossi, M .

CATALYSIS TODAY, 2002, 72 (1-2) :43-49

[4] Formation of acetic acid by aqueous-phase oxidation of ethanol with air in the presence of a heterogeneous gold catalyst [J].

Christensen, Claus H. ;

Jorgensen, Betina ;

Rass-Hansen, Jeppe ;

Egeblad, Kresten ;

Madsen, Robert ;

Klitgaard, Soren K. ;

Hansen, Stine M. ;

Hansen, Mike R. ;

Andersen, Hans C. ;

Riisager, Anders .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (28) :4648-4651

[5] Aerobic oxidation of glucose with gold catalyst: Hydrogen peroxide as intermediate and reagent [J].

Comotti, M ;

Della Pina, C ;

Falletta, E ;

Rossi, M .

ADVANCED SYNTHESIS & CATALYSIS, 2006, 348 (03) :313-316

[6] The catalytic activity of "Naked" gold particles [J].

Comotti, M ;

Della Pina, C ;

Matarrese, R ;

Rossi, M .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (43) :5812-5815

[7] Is the biochemical route always advantageous? The case of glucose oxidation [J].

Comotti, Massimiliano ;

Della Pina, Cristina ;

Falletta, Ermelinda ;

Rossi, Michele .

JOURNAL OF CATALYSIS, 2006, 244 (01) :122-125

[8] Chemical routes for the transformation of biomass into chemicals [J].

Corma, Avelino ;

Iborra, Sara ;

Velty, Alexandra .

CHEMICAL REVIEWS, 2007, 107 (06) :2411-2502

[9] METHYLENECYCLOPROPANE REARRANGEMENT AS A PROBE FOR FREE-RADICAL SUBSTITUENT EFFECTS - SIGMA.-VALUES FOR COMMONLY ENCOUNTERED CONJUGATING AND ORGANOMETALLIC GROUPS [J].

CREARY, X ;

MEHRSHEIKHMOHAMMADI, ME ;

MCDONALD, S .

JOURNAL OF ORGANIC CHEMISTRY, 1987, 52 (15) :3254-3263

[10] Gold in a metallic divided state - From Faraday to present-day nanoscience [J].

Edwards, Peter P. ;

Thomas, John Meurig .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (29) :5480-5486

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