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【结 构 式】 
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【分子编号】10783 【品名】benzyl (2R,4aS,5aR,6R,7R,8R,9S,9aS,10aS)-6-[[(benzyloxy)carbonyl](methyl)amino]-2-(3-butenyl)-4-oxo-4a,7,9-tris[(trimethylsilyl)oxy]decahydro-2H-pyrano[2,3-b][1,4]benzodioxin-8-yl(methyl)carbamate 【CA登记号】 |
【 分 子 式 】C40H58N2O10Si2 【 分 子 量 】783.079 【元素组成】C 61.35% H 7.47% N 3.58% O 20.43% Si 7.17% |
合成路线1
该中间体在本合成路线中的序号：(VI)A new synthesis of trospectomycin has been published: The protection of the amino groups of spectinomycin (I) with benzyl chloroformate gives compound (II), which is treated with trimethylsilylchloride to protect the hydroxyl groups yielding the fully protected compound (III). The reaction of (III) with tert-butyl hydroperoxide makes free the oxo group affording compound (IV), which is converted into the enol ester (V) with allyl chloroformate and LiHMDS. The trans-allylation of (V) in THF by means of Pd under Tsujii conditions gives the protected 3-butenyl derivative (VI), which is finally deprotected and simultaneously hydrogenated with H2 over Pd/Al2O3 in methanol-acetic acid.
| 【1】 Herrinton, P.M.; Hartley, W.M.; Klotz, K.L.; Oxidation and alkylation of spectinomycin derivatives: Synthesis of trospectomycin from spectinomycin. J Org Chem 1993, 58, 3, 678. |
| 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) | 10765 | (2R,4aR,5aR,6S,7S,8R,9S,9aR,10aS)-4a,7,9-Trihydroxy-2-methyl-6,8-bis(methylamino)decahydro-4H-pyrano[2,3-b][1,4]benzodioxin-4-one | C14H24N2O7 | 详情 | 详情 | |
| (II) | 10766 | benzyl (2R,4aR,5aR,6S,7S,8R,9S,9aR,10aS)-6-[[(benzyloxy)carbonyl](methyl)amino]-4a,7,9-trihydroxy-2-methyl-4-oxodecahydro-2H-pyrano[2,3-b][1,4]benzodioxin-8-yl(methyl)carbamate | C30H36N2O11 | 详情 | 详情 | |
| (III) | 10780 | benzyl (2R,4aS,5aR,6S,7S,8R,9S,9aR,10aS)-6-[[(benzyloxy)carbonyl](methyl)amino]-2-methyl-4,4a,7,9-tetrakis[(trimethylsilyl)methyl]-4a,5a,6,7,8,9,9a,10a-octahydro-2H-pyrano[2,3-b][1,4]benzodioxin-8-yl(methyl)carbamate | C46H76N2O7Si4 | 详情 | 详情 | |
| (IV) | 10781 | benzyl (2R,4aR,5aR,6S,7S,8R,9S,9aR,10aS)-6-[[(benzyloxy)carbonyl](methyl)amino]-2-methyl-4-oxo-4a,7,9-tris[(trimethylsilyl)methyl]decahydro-2H-pyrano[2,3-b][1,4]benzodioxin-8-yl(methyl)carbamate | C42H66N2O8Si3 | 详情 | 详情 | |
| (V) | 10782 | (4aS,5aR,6S,7S,8R,9R,9aR,10aR)-6,8-bis[[(benzyloxy)carbonyl](methyl)amino]-2-methylene-4a,7,9-tris[(trimethylsilyl)methyl]-4a,5a,6,7,8,9,9a,10a-octahydro-2H-pyrano[2,3-b][1,4]benzodioxin-4-yl allyl carbonate | C45H66N2O11Si3 | 详情 | 详情 | |
| (VI) | 10783 | benzyl (2R,4aS,5aR,6R,7R,8R,9S,9aS,10aS)-6-[[(benzyloxy)carbonyl](methyl)amino]-2-(3-butenyl)-4-oxo-4a,7,9-tris[(trimethylsilyl)oxy]decahydro-2H-pyrano[2,3-b][1,4]benzodioxin-8-yl(methyl)carbamate | C40H58N2O10Si2 | 详情 | 详情 |