We report the silylation of primary C-H bonds located beta to secondary and tertiary alcohols by exploiting perfluorinated esters as traceless directing groups. The conversion of a secondary or tertiary alcohol to a perfluoroalkyl ester and conversion of the ester to the corresponding silyl acetals by hydrosilylation allows for selective beta-C(sp(3))-H silylation catalyzed by the combination of [Ir(cod)OMe](2) and Me(4)Phen (3,4,7,8-tetramethy1-1,10-phenanthroline) to form 6-membered dioxasilinane. Tamao-Fleming oxidation of these dioxasilinane leads to 1,2 diols. The developed sequence was applied to a series of natural products containing hydroxyl groups.