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Synthetic studies in the 5-thio-D-xylopyranose series: Part 2. Coupling of 5-thio-D-xylopyranosyl donors with electron-rich aryl moieties: Access to C-aryl 5-thio-D-xylopyranosides

Synthetic studies in the 5-thio-D-xylopyranose series: Part 2. Coupling of 5-thio-D-xylopyranosyl donors with electron-rich aryl moieties: Access to C-aryl 5-thio-D-xylopyranosides

Tetrahedron 54(26): 7447-7456

Electron-rich benzene derivatives (anisole, 1,4-dimethoxybenzene) undergo electrophilic substitution by tri-O-acetyl-5-thio-D-xylopyranosyl oxonium ions produced at -78degreeC from the corresponding alpha-trichloroacetimidatc 1 in the presence of BF3.OEt2 complex to yield C-aryl 5-thio-D-xylopyranosides, and in particular, the para-substituted regioisomer in the case of anisole. With the corresponding acetylated 5-thio-alpha-D-xylopyranosyl bromide 2 and the same aromatic compounds, no reaction occurred in the presence of zinc oxide while zinc chloride at room temperature led to tetrahydrothiophene derivatives in moderate to good yields, by a sulfur transannular participation mechanism. With 1,3-diphenol and 1,3,5-triphenol, those sugar derivatives also reacted under quite different conditions (1: -78degreeC, BF3.OEt2, 2: 50degreeC, ZnO) to afford the corresponding C-aryl 5-thio-D-xylopyranosides exclusively. Although O-aryl 5-thio-D-xylopyranosides could not be isolated, their formation as intermediates seemed reasonable under basic conditions only. With acidic catalysts, our observations, in accordance with other results, suggested that C-aryl 5-thio-D-xylopyranosides were formed essentially by electrophilic substitution of electron-rich aromatic derivatives.

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Accession: 009511293

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DOI: 10.1016/s0040-4020(98)00381-0

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