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【结 构 式】 
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【分子编号】59088 【品名】allyl (1R)-1-(2-{[(2S,3R,4R,5S,6R)-3-azido-2-{[tert-butyl(dimethyl)silyl]oxy}-6-({[tert-butyl(dimethyl)silyl]oxy}methyl)-5-hydroxytetrahydro-2H-pyran-4-yl]oxy}ethyl)octyl carbonate 【CA登记号】 |
【 分 子 式 】C32H63N3O8Si2 【 分 子 量 】674.03864 【元素组成】C 57.02% H 9.42% N 6.23% O 18.99% Si 8.33% |
合成路线1
该中间体在本合成路线中的序号：(XXI)Protection of the free hydroxyl of (XVIII) as the allyloxycarbonyl derivative (XIX) was achieved by sequential treatment with phosgene and then with allyl alcohol. Acetonide group hydrolysis in (XIX) under acidic conditions gave diol (XX), which was selectively silylated at the primary hydroxyl group with tert-butyldimethylsilyl chloride and imidazole to afford (XXI). The remaining hydroxyl group of (XXI) was subsequently protected as the allyl carbonate (XXII) with phosgene and allyl alcohol as above. Then, regioselective mono-desilylation of (XXII) with HF provided the desired building block (XXIII).
| 【1】 Christ, W.J.; Kawata, T.; Hawkins, L.D.; Kobayashi, S.; Asano, O.; Rossignol, D.P. (Eisai Co., Ltd.); Anti-endotoxin cpds.. EP 0536969; JP 1993194470; US 5530113 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XVIII) | 59085 | (3R)-1-[((4aR,6S,7R,8R,8aS)-7-azido-6-{[tert-butyl(dimethyl)silyl]oxy}-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-8-yl)oxy]-3-decanol | C25H49N3O6Si | 详情 | 详情 | |
| (XIX) | 59086 | (1R)-1-{2-[((4aR,6S,7R,8R,8aS)-7-azido-6-{[tert-butyl(dimethyl)silyl]oxy}-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-8-yl)oxy]ethyl}octyl allyl carbonate | C29H53N3O8Si | 详情 | 详情 | |
| (XX) | 59087 | allyl (1R)-1-(2-{[(2S,3R,4R,5S,6R)-3-azido-2-{[tert-butyl(dimethyl)silyl]oxy}-5-hydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-4-yl]oxy}ethyl)octyl carbonate | C26H49N3O8Si | 详情 | 详情 | |
| (XXI) | 59088 | allyl (1R)-1-(2-{[(2S,3R,4R,5S,6R)-3-azido-2-{[tert-butyl(dimethyl)silyl]oxy}-6-({[tert-butyl(dimethyl)silyl]oxy}methyl)-5-hydroxytetrahydro-2H-pyran-4-yl]oxy}ethyl)octyl carbonate | C32H63N3O8Si2 | 详情 | 详情 | |
| (XXII) | 59089 | allyl (1R)-1-(2-{[(2R,3S,4R,5R,6S)-3-{[(allyloxy)carbonyl]oxy}-5-azido-6-{[tert-butyl(dimethyl)silyl]oxy}-2-({[tert-butyl(dimethyl)silyl]oxy}methyl)tetrahydro-2H-pyran-4-yl]oxy}ethyl)octyl carbonate | C36H67N3O10Si2 | 详情 | 详情 | |
| (XXIII) | 59009 | N-(1-adamantyl)-N-methylamine; N-methyl-1-adamantanamine | C11H19N | 详情 | 详情 |