Copper/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Mechanistic Assessment of Different Catalyst Systems

被引：222

作者：

Hoover, Jessica M. ^{[1
]}

Ryland, Bradford L. ^{[1
]}

Stahl, Shannon S. ^{[1
]}

机构：

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

来源：

ACS CATALYSIS | 2013年 / 3卷 / 11期

基金：

美国国家卫生研究院; 美国国家科学基金会;

关键词：

alcohol oxidation; aerobic; kinetics; copper; TEMPO; mechanism; FLUOROUS BIPHASIC CATALYSIS; MILD CONDITIONS; STOICHIOMETRIC OXIDANT; SELECTIVE OXIDATION; BENZYLIC ALCOHOLS; ROOM-TEMPERATURE; AQUEOUS AMMONIA; ALDEHYDES; COMPLEXES; NITRILES;

D O I：

10.1021/cs400689a

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：

Combinations of homogeneous Cu salts and 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) have emerged as practical and efficient catalysts for the aerobic oxidation of alcohols. Several closely related catalyst systems have been reported, which differ in the identity of the solvent, the presence of 2,2'-bipyridine as a ligand, the identity of basic additives, and the oxidation state of the Cu source. These changes have a significant influence on the reaction rates, yields, and substrate scope. In this report, we probe the mechanistic basis for differences among four different Cu/TEMPO catalyst systems and elucidate the features that contribute to efficient oxidation of aliphatic alcohols.

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页码：2599 / 2605

页数：7

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