title: A general method for palladium-catalyzed reactions of primary sulfonamides with aryl nonaflates.
abstract: A general method for Pd-catalyzed sulfonamidation of aryl nonafluorobutanesulfonates (aryl nonaflates) is described. A biaryl phosphine ligand, t-BuXPhos, formed the most active catalyst, and K(3)PO(4) in tert-amyl alcohol was found to be the optimal base-solvent combination for the reaction. The reaction conditions were tolerant of various functional groups such as cyano, nitro, ester, aldehyde, ketone, chloride, carbamate, and phenol. Heterocyclic aryl nonaflates were found to be suitable coupling partners. High yields of the coupled products were obtained from the reactions between inherently disfavored substrates such as electron-rich nonaflates and electron-poor sulfonamides. Kinetic data suggest reductive elimination to be the rate-limiting step for the reaction. The only limitation of this methodology that we have identified is the inability of 2,6-disubstituted aryl nonaflates to efficiently participate in the reaction.
authors.affiliation: Abbott Laboratories, Process Research and Development, North Chicago, Illinois 60064, United States. shashank.shekhar@abbott.com
authors.forename: Shashank
authors.initials: S
authors.lastname: Shekhar
authors.forename: Travis B
authors.initials: TB
authors.lastname: Dunn
authors.forename: Brian J
authors.initials: BJ
authors.lastname: Kotecki
authors.forename: Donna K
authors.initials: DK
authors.lastname: Montavon
authors.forename: Steven C
authors.initials: SC
authors.lastname: Cullen
mesh_terms: D002384:Catalysis; D006868:Hydrolysis; D007700:Kinetics; D008024:Ligands; D010165:Palladium / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry; D013449:Sulfonamides / Q000737:chemistry*; D013451:Sulfonic Acids / Q000737:chemistry*
chemical_list: D008024:Ligands; D010720:Phosphines; D013449:Sulfonamides; D013451:Sulfonic Acids; D010165:Palladium; C044646:phosphine