Synthesis of a Library of Xylogluco-Oligosaccharides for Active-Site Mapping of Xyloglucan <i>endo</i>-Transglycosylase FauréRégis Saura-VallsMarc BrumerHarry PlanasAntoni CottazSylvain DriguezHugues 2006 Complex oligosaccharides containing α-d-xylosyl-(1→6)-β-d-glucosyl residues and unsubstituted β-(1→4)-linked d-glucosyl units were readily synthesized using enzymatic coupling catalyzed by the Cel7B E197A glycosynthase from <i>Humicola insolens</i>. Constituting this library required four key steps:  (1) preparing unprotected building blocks by chemical synthesis or enzymatic degradation of xyloglucan polymers; (2) generating the donor synthon in the enzymatic coupling by temporarily introducing a lactosyl motif on the 4-OH of the terminal glucosyl units of the xylogluco-oligosaccharides; (3) synthesizing the corresponding α-fluorides, followed by their de-<i>O</i>-acetylation and the glycosynthase-catalyzed condensation of these donors onto various acceptors; and (4) enzymatically releasing lactose or galactose from the reaction product, affording the target molecules in good overall yields. These complex oligosaccharides proved useful for mapping the active site of a key enzyme in plant cell wall biosynthesis and modification:  the xyloglucan <i>endo</i>-transglycosylase (XET). We also report some preliminary enzymatic results regarding the efficiency of these compounds.