Dehydrative Thioglycosylation of 1‐Hydroxyl Glycosides Catalyzed by In Situ‐Generated AlI3

Thioglycosylation of 1‐hydroxyl glycosides catalyzed by in situ‐generated AlI₃ from elemental aluminium and molecular iodine has been developed. This method provides an alternative route to access anomeric thioglycosides without the use of hazard Lewis acidic activators or per‐modified activated thiol sources. The major advantages of this dehydrative procedure are environmental friendly, ease of operation, high anomeric diastereoselectivity, and mild reaction conditions.