Mechanistic studies of the copper-catalyzed electrophilic amination of O-benzoyl hydroxylamines

ORGN 591

Matthew J. Campbell, mc@unc.edu, Departement of Chemistry, University of North Carolina at Chapel Hill, Campus Box 3290, Venable and Kenan Laboratories, Chapel Hill, NC 27599-3290 and Jeffrey S. Johnson, jsj@unc.edu, Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290.
The mechanism of the copper-catalyzed amination of O-benzoyl hydroxylamines by diorganozinc reagents has been studied. We have ruled out the possibility of radical coupling by establishing that the configuration at the nucleophilic carbon atom is retained during the reaction. The mechanism will also be discussed relative to results from NMR studies and the endocyclic restriction test. After conducting successful experiments with stoichiometrically generated organocuprates from various organometallics, we found we could effect the desired amination using Grignard reagents. This bypasses the need for a stoichiometric equivalent of zinc halide when sensitive functionalities are not present in the reaction partners.
 

Metal-Mediated Reactions and Syntheses
1:00 PM-4:20 PM, Wednesday, March 28, 2007 McCormick Place Lakeside -- Room E350, Level 3, Oral

Division of Organic Chemistry

The 233rd ACS National Meeting, Chicago, IL, March 25-29, 2007