title: 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. Water is found to stabilize the Ni-carbamate catalyst resting state, which thus provides rationalization of the relative decreased rate of coupling of carbamates. Several synthetic applications are presented to showcase the utility of the methodology in the synthesis of polysubstituted aromatic compounds of natural product and bioactive molecule interest.
authors: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
authors: Kyle W
authors: KW
authors: Quasdorf
authors: Aurora
authors: A
authors: Antoft-Finch
authors: Peng
authors: P
authors: Liu
authors: Amanda L
authors: AL
authors: Silberstein
authors: Anna
authors: A
authors: Komaromi
authors: Tom
authors: T
authors: Blackburn
authors: Stephen D
authors: SD
authors: Ramgren
authors: K N
authors: KN
authors: Houk
authors: Victor
authors: V
authors: Snieckus
authors: Neil K
authors: NK
authors: Garg
mesh_terms: D002219:Carbamates / Q000737:chemistry*; D013451:Sulfonic Acids / Q000737:chemistry*
chemical_list: D002219:Carbamates; D013451:Sulfonic Acids; C005741:sulfamic acid