GYKI-39484, RGH-1876

合成路线:The reaction of 1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose (I) with methanesulfonyl chloride and pyridine gives the mesylate (II),which by treatment with sodium azide in DMF is converted into 3-azido-3-deoxy-1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose (III).Selective hydrolysis of (III) with 1N HCl in ethanol affords 3-azido-3-deoxy-1,2-O-isopropylidene-alpha-D-glucofuranose (IV) (1),which is oxidized with sodium metaperiodate to the aldehyde (V).The reduction of (V) with NaBH4 in EtOH gives 3-azido-3-deoxy-1,2-O-isopropylidene-alpha-D-xylofuranose (VI),which is treated with tosyl chloride and pyridine to yield the corresponding 5-O-tosylate (VII) (2).The reaction of (VII) with potassium thiobenzoate (VIII) in hot DMF gives 3-azido-5-S-benzoyl-3-deoxy-1,2-O-isopropylidene-5-thio-alpha-D-xylofuranose (IX),which is treated successively with NaOMe in methanol,to induce cyclization,with refluxing HCl in methanol,to eliminate the isopropylidene group,and finally with acetic anhydride to furnish 1,2,4-tri-O-acetyl-3-azido-3-deoxy-5-thio-D-xylopyranose (X).The condensation of (X) with 4-nitrothiophenol (XI) by means of trimethylsilyl triflate in dichloromethane yields the corresponding acylated dithiopyranoside,which is finally deacetylated with sodium methoxide in methanol.

参考文献标题:Conversion of D-Glucose into d-Oxybiotin.Part I.Synthesis of 2,5-anhydro-3-azido-3-deoxy-D-xylose dimethyl acetal
文献作者:Kuzuhara,H.; Ohrui,H.; Emoto,S.
参考来源:Agr Biol Chem 1970,34(3),375-380


合成路线:The reaction of 1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose (I) with methanesulfonyl chloride and pyridine gives the mesylate (II),which by treatment with sodium azide in DMF is converted into 3-azido-3-deoxy-1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose (III).Selective hydrolysis of (III) with 1N HCl in ethanol affords 3-azido-3-deoxy-1,2-O-isopropylidene-alpha-D-glucofuranose (IV) (1),which is oxidized with sodium metaperiodate to the aldehyde (V).The reduction of (V) with NaBH4 in EtOH gives 3-azido-3-deoxy-1,2-O-isopropylidene-alpha-D-xylofuranose (VI),which is treated with tosyl chloride and pyridine to yield the corresponding 5-O-tosylate (VII) (2).The reaction of (VII) with potassium thiobenzoate (VIII) in hot DMF gives 3-azido-5-S-benzoyl-3-deoxy-1,2-O-isopropylidene-5-thio-alpha-D-xylofuranose (IX),which is treated successively with NaOMe in methanol,to induce cyclization,with refluxing HCl in methanol,to eliminate the isopropylidene group,and finally with acetic anhydride to furnish 1,2,4-tri-O-acetyl-3-azido-3-deoxy-5-thio-D-xylopyranose (X).The condensation of (X) with 4-nitrothiophenol (XI) by means of trimethylsilyl triflate in dichloromethane yields the corresponding acylated dithiopyranoside,which is finally deacetylated with sodium methoxide in methanol.
参考文献标题:Synthese der 3-Amino-3-desoxy- und 3,6-Diamino-3,6-didesoxy-D-glucose
文献作者:Meyer,W.
参考来源:Chem Ber 1968,101(11),3802-07