Po. Whitted et al., Heterolytic cleavage of a beta-phosphatoxyalkyl radical resulting in phosphate migration or radical cation formation as a function of solvent polarity, ORG LETT, 1(1), 1999, pp. 153-156
[GRAPHICS]
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 c
ommon mechanism irrespective of the final products formed, specifically by
initial heterolysis to a radical cation-phosphate anion pair.