RESUMO
Two dinuclear DyIII complexes, [Dy2 (hmb)2 (OTf)2 (H2 O)4 ]â HOTfâ 2 THF (Aâ HOTfâ 2 THF) and [Dy2 (hmi)3 (H2 O)2 ]â 2 HOTf (Bâ 2 HOTf), have been synthesized by the reaction of Dy(OTf)3 and the Schiff-base ligands H2 hmb (N'-(2-hydroxy-3-methoxybenzylidene)benzohydrazide) or H2 hmi ((2-hydroxy-3-methoxyphenyl)methylene isonicotinohydrazine). Disarmed glycosyl trichloroacetimidates can be activated by complexâ A in the synthesis of 1,2-trans-glycosides with primary and secondary acceptors. This method offers an efficient route to selectively deacetylated monosaccharides and disaccharides in high yields and a green catalyst that can be easily recycled and reused.
RESUMO
Dysprosium(III) trifluoromethanesulfonate-catalyzed per-O-acetylation and regioselective anomeric de-O-acetylation of carbohydrates can be tuned by adjusting the reaction medium. In this study, the per-O-acetylation of unprotected sugars by using a near-stoichiometric amount of acetic anhydride under solvent-free conditions resulted in the exclusive formation of acetylated saccharides as anomeric mixtures, whereas anomeric de-O-acetylation in methanol resulted in a moderate-to-excellent yield. Reactions with various unprotected monosaccharides or disaccharides followed by a semi-one-pot sequential conversion into the corresponding acetylated glycosyl hemiacetal also resulted in high yields. Furthermore, the obtained hemiacetals could be successfully transformed into trichloroimidates after Dy(OTf)3 -catalyzed glycosylation.