title: Pd-catalyzed amidation of aryl chlorides using monodentate biaryl phosphine ligands: a kinetic, computational, and synthetic investigation.
abstract: We present results on the amidation of aryl halides and sulfonates utilizing a monodentate biaryl phosphine-Pd catalyst. Our results are in accord with a previous report that suggests that the formation of kappa(2)-amidate complexes is deleterious to the effectiveness of a catalyst for this transformation and that their formation can be prevented by the use of appropriate bidentate ligands. We now provide data that suggest that the use of certain monodentate ligands can also prevent the formation of the kappa(2)-amidate complexes and thereby generate more stable catalysts for the amination of aryl chlorides. Furthermore, computational studies shed light on the importance of the key feature(s) of the biaryl phosphines (a methyl group ortho to the phosphorus center) that enable the coupling to occur. The use of ligands that possess a methyl group ortho to the phosphorus center allows a variety of aryl and heteroaryl chlorides with various amides to be coupled in high yield.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.
authors.forename: Takashi
authors.initials: T
authors.lastname: Ikawa
authors.forename: Timothy E
authors.initials: TE
authors.lastname: Barder
authors.forename: Mark R
authors.initials: MR
authors.lastname: Biscoe
authors.forename: Stephen L
authors.initials: SL
authors.lastname: Buchwald
mesh_terms: D000577:Amides / Q000737:chemistry*; D001190:Arylsulfonates / Q000737:chemistry*; D017605:Bromine Compounds / Q000737:chemistry; D002384:Catalysis; D002712:Chlorides / Q000737:chemistry*; D003198:Computer Simulation; D006571:Heterocyclic Compounds / Q000737:chemistry; D007700:Kinetics; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D010720:Phosphines / Q000138:chemical synthesis / Q000737:chemistry*; D013055:Spectrophotometry, Infrared
chemical_list: D000577:Amides; D001190:Arylsulfonates; D017605:Bromine Compounds; D002712:Chlorides; D006571:Heterocyclic Compounds; D008024:Ligands; D010720:Phosphines; D010165:Palladium; C044646:phosphine