Ligand-modulated palladium oxidation catalysis:: Mechanistic insights into aerobic alcohol oxidation with the Pd(OAc)2/pyridine catalyst system

被引:187
作者
Steinhoff, BA [1 ]
Stahl, SS [1 ]
机构
[1] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA
关键词
D O I
10.1021/ol026988e
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
[GRAPHICS] 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.
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页码:4179 / 4181
页数:3
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