Regio- and Stereoselective Transformations of Sucrose at the Terminal Positions

Chemistry of sucrose emphasizing regio- and stereoselective transformations performed at the terminal positions (C-1′ and/or C-6 and/or C-6′) is reviewed. 2,2′,3,3′,4-Penta-O-benzyl sucrose is proposed as particularly useful substrate for the preparation of modified derivatives such as amines, uronic acids, crown ether analogues with incorporated sucrose backbone, and so-called “higher sucroses”, i.e. compounds elongated at either “end” by up to 9 carbon atoms. Application of benzyl protecting groups makes possible synthesis of free sucrose analogues by simple removing of the protecting groups by hydrogenolysis without affecting the very labile glycosidic bond.