Mechanistic Study of Copper-Catalyzed Aerobic Oxidative Coupling of Arylboronic Esters and Methanol: Insights into an Organometallic Oxidase Reaction

Copper-catalyzed aerobic oxidative coupling of arylboronic acid derivatives and heteroatom nucleophiles is a highly useful method for the formation of aryl-heteroatom bonds. Mechanistic studies reveal that this reaction proceeds via an “oxidase”-style mechanism. Kinetic and spectroscopic studies est...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2009-04, Vol.131 (14), p.5044-5045
Main Authors: King, Amanda E, Brunold, Thomas C, Stahl, Shannon S
Format: Article
Language:English
Subjects:
Boron Compounds - chemistry
Catalysis
Copper - chemistry
Esters - chemistry
Kinetics
Methanol - chemistry
Oxidation-Reduction
Oxygen - chemistry
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Summary:Copper-catalyzed aerobic oxidative coupling of arylboronic acid derivatives and heteroatom nucleophiles is a highly useful method for the formation of aryl-heteroatom bonds. Mechanistic studies reveal that this reaction proceeds via an “oxidase”-style mechanism. Kinetic and spectroscopic studies establish that transmetalation of the aryl group from boron to CuII is the turnover-limiting step and reoxidation of the reduced catalyst by O2 is rapid. Further mechanistic analysis implicates the involvement of an aryl-copper(III) intermediate that undergoes facile C−O bond formation.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja9006657