|
【结 构 式】 
|
【分子编号】45599 【品名】(3R,4R,5S,6R)-6-([[(2S,4S,5S)-4-hydroxy-5-(methylamino)tetrahydro-2H-pyran-2-yl]oxy]methyl)-5-methoxytetrahydro-2H-pyran-2,3,4-triol 【CA登记号】 |
【 分 子 式 】C13H25NO8 【 分 子 量 】323.34344 【元素组成】C 48.29% H 7.79% N 4.33% O 39.58% |
合成路线1
该中间体在本合成路线中的序号：(III)The cyclization of 3,4-bis(3-indolyl)-1-methylpyrroline-2,5-dione (I) by hydrogenation with H2 over Pd/C in DMF, followed by a treatment with TFA, gives the hexacyclic dione (II), which then is condensed with aminosugar (III) in refluxing methanol and dehydrogenated with DDQ in THF to afford the target glycoside.
| 【1】 Van Vranken, D.L.; Chisholm, J.D.; Regiocontrolled synthesis of the antitumor antibiotic AT2433-A1. J Org Chem 2000, 65, 22, 7541. |
| 【2】 Chisholm, J.D.; et al.; A caveat in the application of the excition chirality method to N, N-dialkyl amides. Synthesis and structural revision of AT2433-B1. J Am Chem Soc 1999, 121, 15, 3801. |
| 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) | 41012 | 3,4-di(1H-indol-3-yl)-1-methyl-1H-pyrrole-2,5-dione | 113963-68-1 | C21H15N3O2 | 详情 | 详情 |
| (II) | 45598 | (4bS,4cS,7aS,12bR)-6-methyl-7a,12,12b,13-tetrahydro-4bH-indolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7(4cH,6H)-dione | C21H17N3O2 | 详情 | 详情 | |
| (III) | 45599 | (3R,4R,5S,6R)-6-([[(2S,4S,5S)-4-hydroxy-5-(methylamino)tetrahydro-2H-pyran-2-yl]oxy]methyl)-5-methoxytetrahydro-2H-pyran-2,3,4-triol | C13H25NO8 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(III)The intermediate aminosugar (III) has been obtained as follows: The protection of the alcohol (IV) with Bn-Br and NaH in DMF gives the benzyl ether (V), which is oxidized with OsO4 and NaIO4 in acetone/THF to yield the aldehyde (VI). The cyclization of (VI) by means of TsOH in dioxane/water affords the lactol (VII), which is treated with diethylamino sulfurtrifluoride (DAST) to provide the glycosyl fluoride (VIII). The condensation of (VIII) with the benzylated glucose derivative (IX) by means of AgClO4 and SnCl2 in THF/ethyl ether gives the disaccharide (X). The reduction of the carbamoyl group of (X) with LiAlH4 in refluxing THF yields the methylamino derivative (XI), which is finally debenzylated by hydrogenation over Pd/C in ethanol/THF to afford the target aminosugar (III).
| 【1】 Van Vranken, D.L.; Chisholm, J.D.; Regiocontrolled synthesis of the antitumor antibiotic AT2433-A1. J Org Chem 2000, 65, 22, 7541. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (III) | 45599 | (3R,4R,5S,6R)-6-([[(2S,4S,5S)-4-hydroxy-5-(methylamino)tetrahydro-2H-pyran-2-yl]oxy]methyl)-5-methoxytetrahydro-2H-pyran-2,3,4-triol | C13H25NO8 | 详情 | 详情 | |
| (IV) | 45589 | tert-butyl (4S)-4-(1-hydroxy-3-butenyl)-2,2-dimethyl-1,3-oxazolidine-3-carboxylate | C14H25NO4 | 详情 | 详情 | |
| (V) | 45590 | tert-butyl (4S)-4-[1-(benzyloxy)-3-butenyl]-2,2-dimethyl-1,3-oxazolidine-3-carboxylate | 15930-53-7 | C21H31NO4 | 详情 | 详情 |
| (VI) | 45591 | tert-butyl (4S)-4-[1-(benzyloxy)-3-oxopropyl]-2,2-dimethyl-1,3-oxazolidine-3-carboxylate | C20H29NO5 | 详情 | 详情 | |
| (VII) | 45592 | tert-butyl (3S,4S)-4-(benzyloxy)-6-hydroxytetrahydro-2H-pyran-3-ylcarbamate | C17H25NO5 | 详情 | 详情 | |
| (VIII) | 45593 | tert-butyl (3S,4S)-4-(benzyloxy)-6-fluorotetrahydro-2H-pyran-3-ylcarbamate | C17H24FNO4 | 详情 | 详情 | |
| (IX) | 45594 | [(2R,3S,4S,5R,6R)-4,5,6-tris(benzyloxy)-3-methoxytetrahydro-2H-pyran-2-yl]methanol | C28H32O6 | 详情 | 详情 | |
| (X) | 45595 | tert-butyl (3S,4S,6S)-4-(benzyloxy)-6-[[(2R,3S,4S,5R,6R)-4,5,6-tris(benzyloxy)-3-methoxytetrahydro-2H-pyran-2-yl]methoxy]tetrahydro-2H-pyran-3-ylcarbamate | C45H55NO10 | 详情 | 详情 | |
| (XI) | 45596 | N-((3S,4S,6S)-4-(benzyloxy)-6-[[(2R,3S,4S,5R,6R)-4,5,6-tris(benzyloxy)-3-methoxytetrahydro-2H-pyran-2-yl]methoxy]tetrahydro-2H-pyran-3-yl)-N-methylamine; (3S,4S,6S)-4-(benzyloxy)-N-methyl-6-[[(2R,3S,4S,5R,6R)-4,5,6-tris(benzyloxy)-3-methoxytetrahydro-2H-pyran-2-yl]methoxy]tetrahydro-2H-pyran-3-amine | C41H49NO8 | 详情 | 详情 |