The Philicity of tert-Butoxy Radicals. What Factors Are Important in Determining the Rate and Regiospecificity of tert-Butoxy Radical Addition to Olefins?

Article abstract of DOI:10.1021/jo00268a022

The relative rates of addition of tert-butoxy radicals to substituted styrenes have been evaluated by means of competition experiments.The data demonstrate that tert-butoxy radicals show electrophilic character (ρ = -0.30).An explanation for the apparently anomalous behavior shown by tert-butoxy radicals in their reactions with fluoro olefins is proposed in terms of the ability of α-fluorine substituents to stabilize the incipient C-O bond.