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

TitleMechanistic Study of Copper-Catalyzed Aerobic Oxidative Coupling of Arylboronic Esters and Methanol: Insights into an Organometallic Oxidase Reaction
Publication TypeJournal Article
Year of Publication2009
AuthorsKing, AE, Brunold, TC, Stahl, SS
JournalJournal of the American Chemical Society
Volume131
Pagination5044-+
Date PublishedApr
Accession NumberISI:000265039000017
Keywordsacids, Bond formation, Chemistry, Multidisciplinary, Complexes, cupric acetate, disproportionation, n-arylation, o-2, organic-chemicals
Abstract

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 Cu-II is the turnover-limiting step and reoxidation of the reduced catalyst by O-2 is rapid. Further mechanistic analysis implicates the involvement of an aryl-copper(III) intermediate that undergoes facile C-O bond formation.

Short TitleJ. Am. Chem. Soc.