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An efficient and high yielding reaction for tandem opening of 4,6-O-benzylidene derivatives (gluco, galacto, manno, 2-phthalimido-2-deoxy glucosides) to their corresponding 6-O-acetyl derivatives has been established under metal free condition using 60% solution of aqueous acetic acid (v/v). The reaction is equally pertinent for large scale synthesis and also for disaccharide glycosides. Its application for the construction of a building block towards synthesis of a trisaccharide part related to Pseudomonas aeruginosa utilizing one-pot glycosylation reactions has also been described., (Copyright © 2019. Published by Elsevier Ltd.)