Regioselective acylation of 2′- or 3′-hydroxyl group in salicin: Hemisynthesis of acylated salicins

Abstract

Salicin-based phenolic glycosides(PGs) are important defensive substances against herbivore feeding and have good bioactivities. In this work, a novel approach for the synthesis of salicin-based PGs has been developed, by which PGs of 2′-O-acetylsalicin(5a), 3′-O-acetylsalicin(5b) and 3′-O-benzoylsalicin(5d) were hemisynthesized. The effects of acylation reagent, solvent and temperature on the regioselective acylation of 2′- or 3′-hydroxyl groups of salicin mediated by dibutyltin oxide were investigated. The optimal conditions under which the best regioselectivity reached for 5a–5d were discovered, respectively. Moreover, a tentative tin-oxygen coordination mechanism was put forward to explain the different regioselectivities shown under different conditions.

Keywords

Regioselective acylation / Salicin / Phenolic glycoside / Tin-oxygen coordination / Hemisynthesis

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