Berman AM,
Johnson JS.
* University of North Carolina at Chapel Hill, USA
Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents.
J. Am. Chem. Soc. 2004;
126: 5680-5681
Key words
electrophilic amination - organozinc reagents - copper catalysis
Significance
In 2004, Berman and Johnson developed the first electrophilic amination of N-hydroxylamine benzoates using diorganozinc reagents in the presence of [Cu(OTf)]2·C6H6. This umpolung-type reaction allowed access to a broad range of highly functionalized
secondary and tertiary amines under mild conditions.
Comment
The outstanding performance of N-hydroxylamine benzoates as electrophilic nitrogen sources has inspired various following
publications, opening up new opportunities for amination reactions. Based on experimental
studies, the authors excluded an oxidative addition/reductive elimination pathway
and proposed a SN2-type pathway. For further insights into electrophilic aminations based on this pioneering
work, see: Synthesis 2011, 24, 3954–3964.
