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Direct syntheses of acetylated poly-mannosides can be achieved in one-step starting from a fully acetylated thioglycoside mannosyl donor using a polymerization-type strategy under the correct conditions. Under conditions that allow polymer growth from non-reducing to reducing end (N→R), different acceptor alcohols can be used as the ‘terminating acceptors’ to install different linkers at the reducing terminus. The efficiency is dependent on substituents of the linker, its length, temperature and choice of Lewis acid activator. [ABSTRACT FROM AUTHOR]