The reactions of a series of epoxynitriles and epoxyketones induced by titanocene chloride have been studied. The kinetics of the decyanogenation of β, γ-epoxynitriles with Ti (III) corresponds to a radical reaction (k 25≈ 106 s-1), as demonstrated by competition experiments with H-transfer from 1, 4-cyclohexadiene (1, 4-CHD) or PhSH or conjugate addition to acrylonitrile. The 5-exo cyclization onto nitrile induced by Ti (III) is a radical ...
