Iron-catalyzed generation of α-amino nitriles from tertiary amines

Article abstract of DOI:10.1002/adsc.201300441

The use of iron(II) chloride as catalyst, trimethylsilyl cyanide as source of cyanide ions, and tert-butyl hydroperoxide as oxidant enabled the conversion of aromatic, benzylic, and aliphatic tertiary amines into α-Amino nitriles under mild conditions. Chemoselective functionalization of N-CH₃ to N-CH₂CN was achieved in the presence of Nbenzyl and N-alkyl groups. N,N-Dialkylanilines, PhNR₂, with R=Et, Bu, Bn furnished the alkyl-(aryl)aminoacetonitriles PhN(R)CH₂CN as the main products accompanied by α-Amino nitriles generated by ordinary a-cyanation of the aniline PhNR₂. Formation of PhN(R)CH₂CN was rationalized by oxidative degradation of N,N-dialkylanilines to N-alkylanilines, their condensation with formaldehyde, generated by oxidation of the solvent methanol, and final trapping of the thus formed iminium ions by cyanide.