Synthesis of 2,3-Unsaturated O- and N-Glycosides by HBF₄˙SiO₂-Catalyzed Ferrier Rearrangement of d-Glycals

Abstract

Fluoroboronic acid adsorbed on silica gel (HBF₄˙SiO₂) catalyzes the Ferrier rearrangement of per-O-acetylated glycals with alcohols and sulfonamides to give 2,3-unsaturated O- and N-glycosides in good to excellent yield and with high α-stereoselectivity.

glycosylations - green chemistry - Ferrier rearrangement - N-glycosylsulfonamides - O-glycosides

References and Notes

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Experimental Procedure
To a solution of the glycal (0.5 mmol) and the nucleophile (2 equiv) in dry MeCN (4 mL), the catalyst was added at 40 ˚C. After stirring for the time indicated, the reaction was filtered and the solvent evaporated in vacuo. The residue was chromatographed on SiO₂ (eluent hexane-EtOAc) to afford the glycosides.
Preparation of HBF ₄ ˙SiO ₂
A magnetically stirred suspension of SiO₂ (13.4 g, 230-400 mesh) in Et₂O (37 mL) was treated with 40% aq HBF₄ (1.5 g) for 3 h. The mixture was concentrated and the residue dried under vacuum at 100 ˚C for 24 h to afford HBF₄˙SiO₂ (0.5 mmol g^-¹). [³0]

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The ^¹H NMR (200 MHz) spectra of the glycosides confirmed the α-configuration of the products formed in the reactions by comparison with the literature data.

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