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α-D-Arabinofuranosyl-(1→5)-[α-D-arabinofuranosyl-(1→3)]-α-D-arabinofuranosyl-(1→5)-Darabinofuranose (6) present in motif B of the Mycobacterium tuberculosis cell wall was regio- and stereospecifically synthesized by trichloroacetimidate method. The strategy greatly simplified the procedure for synthesizing 6.