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Herein, we report the oligopeptide-catalyzed site-selective acylation of partially protected monosaccharides. We identified catalysts that invert site-selectivity compared to -methylimidazole, which was used to determine the intrinsic reactivity, for 4,6--protected glucopyranosides (-diols) as well as 4,6--protected mannopyranosides (-diols). The reaction yields up to 81% of the inherently unfavored 2--acetylated products with selectivities up to 15:1 using mild reaction conditions. We also determined the influence of protecting groups on the reaction and demonstrate that our protocol is suitable for one-pot reactions with multiple consecutive protection steps.
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