Stereoselective O‐Glycosylations by Pyrylium Salt Organocatalysis**

Abstract Despite many years of invention, the field of carbohydrate chemistry remains rather inaccessible to non‐specialists, which limits the scientific impact and reach of the discoveries made in the field. Aiming to increase the availability of stereoselective glycosylation chemistry for non‐specialists, we have discovered that several commercially available pyrylium salts catalyze stereoselective O ‐glycosylations of a wide range of phenols and alkyl alcohols. This catalytic reaction utilizes trichloroacetimidates, an easily accessible and synthetically proven electrophile, takes place under air and only initiates when all three reagents are mixed, which should provide better reproducibility by non‐specialists. The reaction exhibits varying degrees of stereospecificity, resulting in β‐selective glycosylations from α‐trichloroacetimidates, whilst an α‐selective glycosylation proceeds from β‐trichloroacetimidates. A mechanistic study revealed that the reaction likely proceeds via an S N 2‐like substitution on the protonated electrophile.