Oxidative cross-coupling processes inspired by the Chan-Lam reaction.

Abstract

The Cu-catalyzed oxidative cross-coupling of N- and O-nucleophiles with aryl boronic acids (the Chan-Lam reaction) remains among the most useful approaches to prepare aniline and phenol derivatives. The combination of high chemoselectivity, mild reaction conditions, and the ability to use simple Cu-salts as catalysts makes this process a valuable alternative to aromatic substitutions and Pd-catalyzed reactions of aryl electrophiles (Buchwald-Hartwig coupling). Despite the widespread use of Chan-Lam reactions in synthesis, the analogous carbon-carbon bond forming variant of this process had not been developed prior to our work. This feature article describes our discovery and application of Cu-catalyzed oxidative coupling reactions of activated methylene derivatives or carboxylic acids with nucleophiles including aryl boronic esters and amines.