Facile amine formation by intermolecular catalytic amidation of carbon-hydrogen bonds.
A simple copper-based catalytic system has been developed for the carbon-hydrogen amidation reaction. The copper-homoscorpionate complex Tp(Br3)Cu(NCMe) catalyzes the transfer of the nitrene unit NTs (Ts = p-toluenesulfonyl) and its subsequent insertion into the sp(3) C-H bonds of alkyl aromatic and cyclic ethers or the sp(2) C-H bonds of benzene using PhI=NTs as the nitrene source, affording the corresponding trisubstitued NR(1)HTs amines in moderate to high yields. The use of the environmentally friendly chloramine-T has also proven effective, with the advantage that sodium chloride is formed as the only byproduct. A tandem, one-pot consecutive nitrene-carbene insertion system has been developed to yield amino acid derivatives.
Fructos
Manuel R
MR
Laboratorio de Catalisis Homogénea, Departamento de Química y Ciencia de los Materiales, Unidad Asociada al CSIC, Universidad de Huelva, Campus de El Carmen, 21007-Huelva, Spain.
Trofimenko
Swiatoslaw
S
Díaz-Requejo
M Mar
MM
Pérez
Pedro J
PJ