Heterolytic cleavage of a β-phosphatoxyalkyl radical resulting in phosphate migration or radical cation formation as a function of solvent polarity

Article abstract of DOI:10.1021/ol990054h

(Equation Presented) The 2-(diethylphosphatoxy)-2-(p-methoxyphenyl)-1,1-dimethylethyl radical (1) reacted to give the benzylic radical product from phosphate migration or a radical cation (or a mixture of the two) as a function of solvent. Smooth acceleration in rates of reactions of 1 in solvents of increasing polarity and consistent entropies of activation indicate that radical 1 reacts by common mechanism irrespective of the final products formed, specifically by initial heterolysis to a radical cation-phosphate anion pair.