A Highly Selective Pd(OAc)2/Pyridine/K2CO3 System for Oxidation of Terpenic Alcohols by Dioxygen

被引：10

作者：

Carari, Danieli M. ^{[1
]}

da Silva, Marcio J. ^{[1
]}

机构：

[1] Univ Fed Vicosa, Dept Quim, BR-35690000 Vicosa, MG, Brazil

来源：

CATALYSIS LETTERS | 2012年 / 142卷 / 02期

关键词：

Palladium; Terpenic alcohol; Nitrogen ligand; Dioxygen; PALLADIUM-CATALYZED OXIDATION; PALLADIUM(II)-CATALYZED OXIDATION; AEROBIC OXIDATION; KETONES; IDENTIFICATION; CARBONYLATION; ALDEHYDES; ALKENES; SCOPE;

D O I：

10.1007/s10562-011-0754-4

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：

Molecular sieves, complex organic bases and radical oxidants are commonly used in alcohols oxidation reactions. In this work, we have evaluated the beneficial effects of addition of K2CO3 to Pd(II)-catalyzed oxidation alcohols, which resulted in a remarkable increase in the oxidation reaction rates without selectivity losses. Herein, in a metallic reoxidant-free system, terpenic alcohols (beta-citronellol, nerol and geraniol) were selectively converted into respective aldehydes from Pd(II)-catalyzed oxidation reactions in presence of dioxygen. High conversions and selectivities (greater than 90%) were achieved in the presence of the Pd(OAc)(2)/K2CO3 catalyst and pyridine excess. The exogenous role of others auxiliary anionic and nitrogen compounds was appraised.

引用

页码：251 / 258

页数：8

共 36 条

[1] PALLADIUM-HYDROQUINONE CATALYZED ELECTROCHEMICAL 1,4-OXIDATION OF CONJUGATED DIENES [J].

BACKVALL, JE ;

GOGOLL, A .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1987, (16) :1236-1238

[2] Palladium-catalyzed enantioselective oxidation of alcohols:: A dramatic rate acceleration by Cs2CO3/t-BuOH [J].

Bagdanoff, JT ;

Ferreira, EM ;

Stoltz, BM .

ORGANIC LETTERS, 2003, 5 (06) :835-837

[3] C-C, C-O, C-N bond formation on sp2 carbon by Pd(II)-catalyzed reactions involving oxidant agents [J].

Beccalli, Egle M. ;

Broggini, Gianluigi ;

Martinelli, Michela ;

Sottocornola, Silvia .

CHEMICAL REVIEWS, 2007, 107 (11) :5318-5365

[4] Palladium-Catalyzed Carbonylation Reactions of Alkenes and Alkynes [J].

Brennfuehrer, Anne ;

Neumann, Helfried ;

Beller, Matthias .

CHEMCATCHEM, 2009, 1 (01) :28-41

[5] Discovery of a practical direct O2-coupled Wacker oxidation with Pd[(-)-sparteine]Cl2 [J].

Cornell, Candace N. ;

Sigman, Matthew S. .

ORGANIC LETTERS, 2006, 8 (18) :4117-4120

[6] Pd(OAC)2/M(NO3)n (M = Cu(II), Fe(III); n=2, 3): Kinetic investigations of an alternative Wacker system for the oxidation of natural olefins [J].

da Silva, Marcio J. ;

Teixeira, Robson Ricardo ;

Carari, Danielli Marcolan .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2009, 694 (20) :3254-3261

[7] Palladium-catalyzed oxidation of monoterpenes: novel tandem oxidative coupling-oxidation of camphene by dioxygen [J].

da Silva, MJ ;

Gusevskaya, EV .

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2001, 176 (1-2) :23-27

[8] Palladium-Catalysed Oxidation of Bicycle Monoterpenes by Hydrogen Peroxide in Acetonitrile Solutions: A Metal Reoxidant-Free and Environmentally Benign Oxidative Process [J].

de Oliveira, Alexandre Almeida ;

da Silva, Milene Lopes ;

da Silva, Marcio Jose .

CATALYSIS LETTERS, 2009, 130 (3-4) :424-431

[9] The palladiuim-catalyzed oxidative kinetic resolution of secondary alcohols with molecular oxygen [J].

Ferreira, EM ;

Stoltz, BM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (31) :7725-7726

[10] Catalytic routes from renewables to fine chemicals [J].

Gallezot, Pierre .

CATALYSIS TODAY, 2007, 121 (1-2) :76-91

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