|
【结 构 式】 
|
【分子编号】38931 【品名】(3aR,5S,6S,6aR)-6-azido-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxole; (3aR,5S,6S,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-6-yl azide 【CA登记号】 |
【 分 子 式 】C12H19N3O5 【 分 子 量 】285.30008 【元素组成】C 50.52% H 6.71% N 14.73% O 28.04% |
合成路线1
该中间体在本合成路线中的序号：(III)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.
| 【1】 Meyer, W.; Synthese der 3-Amino-3-desoxy- und 3,6-Diamino-3,6-didesoxy-D-glucose. Chem Ber 1968, 101, 11, 3802-07. |
| 【2】 Kuzuhara, H.; Ohrui, H.; Emoto, S.; Conversion of D-Glucose into d-Oxybiotin. Part I. Synthesis of 2,5-anhydro-3-azido-3-deoxy-D-xylose dimethyl acetal. Agr Biol Chem 1970, 34, 3, 375-380. |
| 【3】 Kovácsné Bozó, E.; Kuszmann, J.; Szabó, G.; Boros, S.; Moravcsik, I. (Gedeon Richter Ltd.); Novel anticoagulant glycosides and pharmaceutical compsns. thereof. EP 0907656; WO 9749716 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (I) | 29141 | (3aR,5S,6S,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-6-ol | 582-52-5 | C12H20O6 | 详情 | 详情 |
| (II) | 38930 | (3aR,5R,6R,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-6-[[methyl(dimethylene)-lambda(6)-sulfanyl]oxy]tetrahydrofuro[2,3-d][1,3]dioxole | C15H26O6S | 详情 | 详情 | |
| (III) | 38931 | (3aR,5S,6S,6aR)-6-azido-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxole; (3aR,5S,6S,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-6-yl azide | C12H19N3O5 | 详情 | 详情 | |
| (IV) | 38932 | (1R)-1-[(3aR,5S,6S,6aR)-6-azido-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-1,2-ethanediol | C9H15N3O5 | 详情 | 详情 | |
| (V) | 38933 | (3aR,5S,6S,6aR)-6-azido-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxole-5-carbaldehyde | C8H11N3O4 | 详情 | 详情 | |
| (VI) | 38934 | [(3aR,5S,6S,6aR)-6-azido-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-5-yl]methanol | C8H13N3O4 | 详情 | 详情 | |
| (VII) | 38935 | [(3aR,5S,6S,6aR)-6-azido-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-5-yl]methyl 4-methylbenzenesulfonate | C15H19N3O6S | 详情 | 详情 | |
| (VIII) | 38936 | potassium benzenecarbothioate | C7H5KOS | 详情 | 详情 | |
| (IX) | 38937 | S-[[(3aR,5S,6S,6aR)-6-azido-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-5-yl]methyl] benzenecarbothioate | C15H17N3O4S | 详情 | 详情 | |
| (X) | 38938 | (2R,3R,4S,5S)-2,5-bis(acetoxy)-4-azidotetrahydro-2H-thiopyran-3-yl acetate | C11H15N3O6S | 详情 | 详情 | |
| (XI) | 38898 | 4-nitrophenylhydrosulfide; 4-nitrobenzenethiol | 1849-36-1 | C6H5NO2S | 详情 | 详情 |
| (XII) | 38939 | (2S,3R,4S,5S)-5-(acetoxy)-4-azido-2-[(4-nitrophenyl)sulfanyl]tetrahydro-2H-thiopyran-3-yl acetate | C15H16N4O6S2 | 详情 | 详情 |