Gold-Catalyzed Direct C(sp3)-H Acetoxylation of Saturated Hydrocarbons

In this communication we report our studies towards the development of a gold-catalyzed direct acetoxylation of C(sp(3))-H bonds. We achieve this through the use of the hypervalent iodine reagent PhI(OAc)(2) in combination with a simple gold salt (HAuBr4) as the catalyst. Through a comparison of the reactivities of cyclooctane and adamantane we judge the reaction to proceed via hydride transfer. This is further substantiated through computational studies of the relative energies for the anions, radicals and cations derived from C-H bond cleavage of cyclooctane and adamantane relevant to the C-H cleaving step.