Acyloxyalkyl radicals

UB3LYP/6-31G(d) level of theory using the NPA scheme, (b) The same data as those in (a) represented as differences in charge and spin densities between ground states 3 and transition states 6 and 7. The additional data point symbolized with an open circle corresponds to the difference between protonated systems 9 and 10.14 

Even though the magnitude of the proton-induced barrier reduction calculated here might not be attainable under solution phase conditions, this result still suggests that acid catalysis might play a significant role under some circumstances. 

---

The 1,2-acyloxy migration in /3-acyloxyalkyl radicals has been the subject of many experimental3 as well as some theoretical studies.4,17 While a broad spectrum of mechanisms is conceivable for this kind of process,3 only three will be discussed here in detail (Scheme 4) (i) stepwise heterolysis/recombination involving... 

A computational study on the mechanism of rearrangements of yS-acyloxyalkyl radicals has been performed Zipse, H. J. Am. Chem. Soc. 1997, 119, 1087. 

---