Combee LA.
Raya B.
Wang D.
Hilinski MK.
* University of Virginia, Charlottesville, USA
Organocatalytic Nitrenoid Transfer: Metal-Free Selective Intermolecular C(sp
3)–H Amination Catalyzed by an Iminium Salt.
Chem. Sci. 2018;
DOI:
10.1039/C7SC03968A
Key words
nitrenoid transfer - amination - iminium salt
Significance
The Hilinski group reports a C(sp3)–H amination through a nitrenoid transfer catalyzed by iminium salt A. The reaction proceeds in moderate to high yields, and the method is applicable to
several natural products having other functional groups.
Comment
In contrast to reported nitrenoid-transfer reactions catalyzed by transition metals,
the authors developed an organocatalytic variant of the transformation. They proposed
the diaziridinium salt as critical intermediate, which is supported by ESI-MS analysis,
but not yet fully characterized. A kinetic isotopic effect study suggested C–H cleavage
as the rate-determining step.