Suzuki-Miyaura cross-coupling of aryl carbamates and sulfamates: experimental and computational studies.

ABSTRACT: The first Suzuki-Miyaura cross-coupling reactions of the synthetically versatile aryl O-carbamate and O-sulfamate groups are described. The transformations utilize the inexpensive, bench-stable catalyst NiCl(2)(PCy(3))(2) to furnish biaryls in good to excellent yields. A broad scope for this methodology has been demonstrated. Substrates with electron-donating and electron-withdrawing groups are tolerated, in addition to those that possess ortho substituents. Furthermore, heteroaryl substrates may be employed as coupling partners. A computational study providing the full catalytic cycles for these cross-coupling reactions is described. The oxidative addition with carbamates or sulfamates occurs via a five-centered transition state, resulting in the exclusive cleavage of the aryl C-O bond. W

SUBMITTER: Quasdorf KW 

PROVIDER: S-EPMC3091075 | biostudies-literature | 2011 Apr

REPOSITORIES: biostudies-literature