Acetolysis is a widely used reaction in both synthetic and analytical carbohydrate chemistry.1 Its main synthetic application is to convert alkyl or aryl glycosides into 1-O-acetylated derivatives, which are useful building blocks easily transformable into other derivatives. Owing to the importance of acetolysis of carbohydrates in synthetic glycochemistry, several studies on the mechanism of this reaction exist in the literature.2 There are no general protocols for acetolysis, and the conditions are often optimized for each compound, especially when mild and/or selective reactions are required.