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Synfacts 2007(7): 0752-0752
DOI: 10.1055/s-2007-968646
DOI: 10.1055/s-2007-968646
Metal-Mediated Synthesis
© Georg Thieme Verlag Stuttgart · New York
Mechanistic Studies of the Cu(II)-Catalyzed Electrophilic Amination
M. J. Campbell, J. S. Johnson*
University of North Carolina at Chapel Hill, USA
Further Information
Publication History
Publication Date:
22 June 2007 (online)
Significance
These studies are a valuable contribution to the field of electrophilic amination of non-stabilized carbanions. Evidence was found that the Cu(II)-catalyzed amination of dialkylzinc reagents follows an SN2 pathway, as the presence of Zn(II) was not essential in the C-N bond-forming step and the reaction proceeded with retention of the configuration at the reacting carbon. In an endocyclic restriction test, the amination was shown to occur intermolecularly supporting a transition state that has a large Cu-N-OBz bond angle. The rates of the transmetallation to Cu and the C-N bond formation were found to exceed the rates of O-acylation.