Organocatalysis applied to carbohydrates: from roots to current developments.

Organocatalysis emerged in the last decade as a powerful tool for the synthesis of complex molecules. In the field of carbohydrates, it found widespread use in the synthesis of rare and non-natural carbohydrate derivatives. Additionally, it has also found important application in the stereoselective functionalization of the anomeric carbon in glycosylation reactions. These efforts culminated in the development of different types of catalysts operating through distinct activation modes that allow the selective synthesis of α- or ß-glycosides even on daunting substrates. All these advances starting from its first examples in carbohydrate synthesis to the current developments in glycosylation reactions are reviewed.