The role of chelating diamine ligands in the goldberg reaction: a kinetic study on the copper-catalyzed amidation of aryl iodides.
The mechanistic details of the Cu-catalyzed amidation of aryl iodides are presented. The kinetic data suggest that the diamine ligand prevents multiple ligation of the amide. The formation of an amidocuprate species external to the catalytic cycle helped to rationalize the dependence on diamine concentration and the inverse dependence on amide concentration at low diamine concentrations. The intermediacy of a Cu(I) amidate was established through both its chemical and kinetic competency.
Strieter
Eric R
ER
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Blackmond
Donna G
DG
Buchwald
Stephen L
SL
D000577:Amides / Q000138:chemical synthesis*; D002384:Catalysis; D002614:Chelating Agents / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D003959:Diamines / Q000737:chemistry*; D007462:Iodobenzenes / Q000737:chemistry*; D007700:Kinetics; D008024:Ligands
D000577:Amides; D002614:Chelating Agents; D003959:Diamines; D007462:Iodobenzenes; D008024:Ligands; D003300:Copper