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【结 构 式】 
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【分子编号】62596 【品名】4-{(3S,6R,7S,8S,12Z,15S,16E)-3,7-bis{[tert-butyl(dimethyl)silyl]oxy}-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxo-15-[(triethylsilyl)oxy]-12,16-heptadecadienoyl}-3lambda~6~-thia-4-azatricyclo[5.2.1.0~1,5~]decane-3,3-dione 【CA登记号】 |
【 分 子 式 】C53H96N2O7S2Si3 【 分 子 量 】1021.74302 【元素组成】C 62.3% H 9.47% N 2.74% O 10.96% S 6.28% Si 8.25% |
合成路线1
该中间体在本合成路线中的序号：(VII)The aldol condensation of 2,2-dimethyl-3-oxopentanal (I) with acetylsultam (II) by means of Et3B/OTf and DIEA gives the aldol adduct (III), which is treated with Tbdms-OTf to yield the silyl ether (IV). The TiCl4 catalyzed aldol reaction between ketone (IV) with the intermediate aldehyde (V) affords the aldol adduct (VI), which is treated with Tbdms-OTf to provide the silylated adduct (VII). Finally the cleavage of the sultam group of (VII) by means of LiO2H furnishes the already known carboxylic acid intermediate (VIII)
| 【1】 Altmann, K.-H.; et al.; The total synthesis and biological assessment of trans-epothilone A. Helv Chim Acta 2002, 85, 11, 4086. |
| 【2】 Koch, G.; Loiseleur, O.; Fuentes, D.; Jantsch, A.; Altmann, K.-H.; Diastereoselective titanium enolate aldol reaction for the total synthesis of epothilones. Org Lett 2002, 4, 22, 3811. |
| 【3】 Nicolaou, K.C.; et al.; Total syntheses of epothilones A and B via a macrolactonization-based strategy. J Am Chem Soc 1997, 119, 34, 7974. |
| 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) | 44448 | 2,2-dimethyl-3-oxopentanal | C7H12O2 | 详情 | 详情 | |
| (II) | 62591 | 4-acetyl-3lambda~6~-thia-4-azatricyclo[5.2.1.0~1,5~]decane-3,3-dione | C10H15NO3S | 详情 | 详情 | |
| (III) | 62592 | 4-[(3S)-3-hydroxy-4,4-dimethyl-5-oxoheptanoyl]-3lambda~6~-thia-4-azatricyclo[5.2.1.0~1,5~]decane-3,3-dione | C17H27NO5S | 详情 | 详情 | |
| (IV) | 62593 | 4-((3S)-3-{[tert-butyl(dimethyl)silyl]oxy}-4,4-dimethyl-5-oxoheptanoyl)-3lambda~6~-thia-4-azatricyclo[5.2.1.0~1,5~]decane-3,3-dione | C23H41NO5SSi | 详情 | 详情 | |
| (V) | 62594 | (2S,6Z,9S,10E)-2,6,10-trimethyl-11-(2-methyl-1,3-thiazol-4-yl)-9-[(triethylsilyl)oxy]-6,10-undecadienal | C24H41NO2SSi | 详情 | 详情 | |
| (VI) | 62595 | 4-{(3S,6R,7S,8S,12Z,15S,16E)-3-{[tert-butyl(dimethyl)silyl]oxy}-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxo-15-[(triethylsilyl)oxy]-12,16-heptadecadienoyl}-3lambda~6~-thia-4-azatricyclo[5.2.1.0~1,5~]decane-3,3-dione | C47H82N2O7S2Si2 | 详情 | 详情 | |
| (VII) | 62596 | 4-{(3S,6R,7S,8S,12Z,15S,16E)-3,7-bis{[tert-butyl(dimethyl)silyl]oxy}-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxo-15-[(triethylsilyl)oxy]-12,16-heptadecadienoyl}-3lambda~6~-thia-4-azatricyclo[5.2.1.0~1,5~]decane-3,3-dione | C53H96N2O7S2Si3 | 详情 | 详情 | |
| (VIII) | 62597 | (3S,6R,7S,8S,12Z,15S,16E)-3,7-bis{[tert-butyl(dimethyl)silyl]oxy}-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxo-15-[(triethylsilyl)oxy]-12,16-heptadecadienoic acid | C45H85NO6SSi3 | 详情 | 详情 |