Efficient and selective aerobic oxidation of alcohols into aldehydes and ketones using ruthenium/TEMPO as the catalytic system

被引：519

作者：

Dijksman, A ^{[1
]}

Marino-González, A ^{[1
]}

Payeras, AMI ^{[1
]}

Arends, IWCE ^{[1
]}

Sheldon, RA ^{[1
]}

机构：

[1] Delft Univ Technol, Organ Chem & Catalysis Lab, Dept Biotechnol, NL-2628 BL Delft, Netherlands

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2001年 / 123卷 / 28期

关键词：

D O I：

10.1021/ja0103804

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The combination of RuC2(PPh3)(3) and TEMPO affords an efficient catalytic system for the aerobic oxidation of a variety of primary and secondary alcohols, giving the corresponding aldehydes and ketones, in > 99% selectivity in all cases. The Ru/TEMPO system displayed a preference for primary vs secondary alcohols. Results from Hammett correlation studies (p = -0.58) and the primary kinetic isotope effect (k(H)/k(D) = 5.1) for the catalytic aerobic benzyl alcohol oxidations are inconsistent with either an oxoruthenium (O=Ru) or an oxoammonium based mechanism. We postulate a hydridometal mechanism, involving a "RuH2(PPh3)(3)" species as the active catalyst. TEMPO acts as a hydrogen transfer mediator and is either regenerated by oxygen, under catalytic aerobic conditions, or converted to TEMPH under stoichiometric anaerobic conditions.

引用

页码：6826 / 6833

页数：8

共 74 条

[1]

ANELLI PL, 1987, J ORG CHEM, V52, P2559

[2] Evidence for a ruthenium dihydride species as the active catalyst in the RuCl2(PPh3)-catalyzed hydrogen transfer reaction in the presence of base [J].

Aranyos, A ;

Csjernyik, G ;

Szabó, KJ ;

Bäckvall, JE .

CHEMICAL COMMUNICATIONS, 1999, (04) :351-352

[3] RUTHENIUM-CATALYZED ISOMERIZATION OF ALLYLIC ALCOHOLS TO SATURATED KETONES [J].

BACKVALL, JE ;

ANDREASSON, U .

TETRAHEDRON LETTERS, 1993, 34 (34) :5459-5462

[4] STUDIES ON TRANSITION-METAL OXO AND NITRIDO COMPLEXES .13. PERRUTHENATE AND RUTHENATE ANIONS AS CATALYTIC ORGANIC OXIDANTS [J].

BAILEY, AJ ;

GRIFFITH, WP ;

MOSTAFA, SI ;

SHERWOOD, PA .

INORGANIC CHEMISTRY, 1993, 32 (03) :268-271

[5] USE OF RUTHENIUM TETROXIDE AS A MULTI-PURPOSE OXIDANT [J].

BERKOWITZ, LM ;

RYLANDER, PN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1959, 80 (24) :6682-6684

[6] THE SELECTIVE OXIDATION OF PRIMARY ALCOHOLS TO ALDEHYDES BY O-2 EMPLOYING A TRINUCLEAR RUTHENIUM CARBOXYLATE CATALYST [J].

BILGRIEN, C ;

DAVIS, S ;

DRAGO, RS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (12) :3786-3787

[7] Modified mesoporous silicate MCM-41 materials: immobilised perruthenate - a new highly active heterogeneous oxidation catalyst for clean organic synthesis using molecular oxygen [J].

Bleloch, A ;

Johnson, BFG ;

Ley, SV ;

Price, AJ ;

Shephard, DS ;

Thomas, AW .

CHEMICAL COMMUNICATIONS, 1999, (18) :1907-1908

[8]

BOBBITT JM, 1988, HETEROCYCLES, V27, P509

[9] TEMPO oxidations with a silica-supported catalyst [J].

Bolm, C ;

Fey, T .

CHEMICAL COMMUNICATIONS, 1999, (18) :1795-1796

[10] Catalytic synthesis of aldehydes and ketones under mild conditions using TEMPO/Oxone [J].

Bolm, C ;

Magnus, AS ;

Hildebrand, JP .

ORGANIC LETTERS, 2000, 2 (08) :1173-1175

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