Base‐Promoted Glycosylation Allows Protecting Group‐Free and Stereoselective O‐Glycosylation of Carboxylic Acids**

Here we report a simple and general method to achieve fully unprotected, stereoselective glycosylation of carboxylic acids, employing bench-stable allyl glycosyl sulfones as donors. Running the glycosylation reaction under basic conditions was crucial for the efficiencies and selectivities. Both the donor activation stage and the glycosidic bond forming stage of the process are compatible with free hydroxyl groups, thereby allowing for the use of fully unprotected glycosyl donors. This transformation is stereoconvergent, occurs under mild and metal-free conditions at ambient temperature with visible light (455 nm) irradiation, and displays remarkable scope with respect to both reaction partners. Many natural products and commercial drugs, including an acid derived from the complex anticancer agent taxol, were efficiently glycosylated. Experimental studies provide insights into the origin of the stereochemical outcome.