The envisioned synthetic technology was achieved by devising a redox-active tethering group that can be regioselectively appended to the unprotected sugar and then transformed into a readily-removable protecting group upon the photoredox-mediated C-functionalization reaction (Fig. ). Leveraging the known ability of sterically encumbered chlorosilanes to selectively append to the primary alcohol functionality in unprotected sugars, we identified (iodomethyl)diisopropylsilyl as the prime candidate for the desired redox-active tethering group (Fig. ). While this group has typically been employed in manifolds involving intramolecular HAT promoted by light-mediated palladium and copper catalysis, we sought to realize the envisioned reactivity under more benign photoredox conditions in the absence of metal-based co-catalysts. In the proposed mechanistic sequence, the C-I bond in the tethering group is activated through either one-electron reduction or halogen atom transfer (XAT) promoted by photoredox catalysis, leading to the key α-silyl C-radical intermediate. This radical was envisioned to undergo intramolecular HAT with one of the endocyclic C-H bonds in the sugar, followed by addition of the resulting α-oxyl C-radical to an appropriate radical acceptor (somophile) to furnish the desired C-functionalized product. Notably, as the result of the outlined sequence, the tethering group is transformed into a trivial diisopropylmethylsilyl protecting group, which can be easily removed from the C-functionalized product, while facilitating its purification.