A highly regioselective hydrogenolysis of the anomeric benzyl group is reported. The reaction involves selective acetolysis of benzyl acetals of various mono‐ and di‐saccharides using 10 % Pd/C under hydrogen atmosphere in the presence of Na2CO3. The generality of the methodology is evaluated by applying it to a number of perbenzylated/orthogonally protected benzyl glycosides.

An unusual 1,5‐ or 1,6‐alkyl transposition along with acetalization of 3‐deoxy glycals is reported. TMSOTf was used as the Lewis acid for carrying out the transformation. A plausible mechanism is proposed. The novel method provided access to 2‐C‐branched bicyclic acetals of various deoxy‐sugar derivatives as well as 2‐C‐branched levoglycosan derivatives.

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