Steinhoff Bradley A, Stahl Shannon S
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706, USA.
Org Lett. 2002 Nov 14;4(23):4179-81. doi: 10.1021/ol026988e.
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.
醋酸钯（II）：吡啶（1:4）是一种用于分子氧氧化醇类的高效催化体系。对该反应的机理研究表明，吡啶促进钯（0）的有氧氧化，但抑制钯（II）对醇的氧化。动力学结果表明，限速底物氧化包括（i）钯（II）-醇盐的形成、（ii）吡啶解离和（iii）β-氢消除。这些结果为设计和/或筛选更有效的有氧氧化催化剂提供了一个框架。
