Stoichiometric and catalytic hydroamination of alkynes and allene by zirconium bisamides Cp2Zr(NHR)2

The synthesis of enamines and imines from the hydroamination of alkynes and allene catalyzed by Cp2Zr(NHR)2 was reported. A first-order reaction with respect to the bisamide and alkyne and an inverse first order in amine were deduced from examination of the reaction of 2,6-dimethylaniline and diphenylacetylene in the presence of the zirconium bisamide. A mechanism based from kinetic and stoichiometric results proposed the intermediacy of Cp2Zr=NR complex, azametallacyclobutenes and an enamide amide.