Remote Hydroxylation through Radical Translocation and Polar Crossover

Mild conditions are reported for the hydroxylation of aliphatic CH bonds through radical translocation, oxidation to carbocation, and nucleophilic trapping with H2O. This remote functionalization employs fac-[Ir(ppy)(3)] together with Tz(o) sulfonate esters and sulfonamides to facilitate the site-selective replacement of relatively inert CH bonds with the more synthetically useful COH group. The hydroxylation of a range of substrates and the methoxylation of two substrates through 1,6- and 1,7-hydrogen-atom transfer are demonstrated. In addition, a synthesis of the antidepressant fluoxetine using remote hydroxylation as a key step is presented.