Advances in synthetic methodologies are essential to increase the share of natural products and their derivatives in modern drug discovery screening efforts. However, the derivatization of these molecules is challenging due to their complexity. One of the approaches to address this problem is to conduct site-selective C–H functionalization reactions. Among the possible C–H functionalization reactions, the borylation and silylation of C–H bonds are particularly valuable because of the potential of groups based on silicon and boron to undergo cross-coupling or oxidative functionalization reactions.The hydroxyl group is the most commonly encountered functional group in natural compounds, making alcohol-directed C–H functionalization particularly important for the latestage functionalization of complex molecules. We have developed an Ir-catalyzed functionalization of primary beta-C(sp3)–H bonds of tertiary and secondary alcohols enabled by traceless directing groups. The targeted alcohol is transformed into a perfluorinated ester and then reduced with diethyl silane. This silyl acetal directs the C–H silylation reaction to obtain the six-membered dioxasilinanes. Tamao-Fleming oxidation of these oxasilolanes leads to the formation of 1,2-diols. The developed sequence was applied to a series of natural products derivatives containing hydroxyl groups.