On the mechanism and kinetics of radical reactions of epoxyketones and epoxynitriles induced by titanocene chloride

A Fernández-Mateos, P Herrero Teijón…

Index: Fernandez-Mateos; Herrero Teijon; Mateos Buron; Rabanedo Clemente; Rubio Gonzalez Journal of Organic Chemistry, 2007 , vol. 72, # 26 p. 9973 - 9982

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Citation Number: 40

Abstract

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 ...