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【结 构 式】 
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【分子编号】52611 【品名】4,8-bis{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-16-(1-hydroxyethyl)-5,5,7,9-tetramethyloxa-13-cyclohexadecene-2,6-dione 【CA登记号】 |
【 分 子 式 】C33H64O6Si2 【 分 子 量 】613.03856 【元素组成】C 64.66% H 10.52% O 15.66% Si 9.16% |
合成路线1
该中间体在本合成路线中的序号：(XXII)The macrolactonization of (XXII) under Yamaguchi conditions (2,4,6-trichlorobenzoyl chloride), followed by selective desilylation with H2SiF6, gives the macrolactone (XXII). The oxidation of the secondary OH group of (XXII) with (COCl)2 and TEA in DMSO/dichloromethane yields the ketone (XXIII), which is submitted to a Wadsworth-Emmons condensation with the phosphonate (XXIV) by means of BuLi in THF to afford the protected precursor (XXV). Elimination of the silyl protecting groups of (XXV) with TFA in dichloromethane affords the free precursor (XXVI), which is finally epoxidated with methyl(trifluoromethyl)dioxirane (MTFDO) in acetonitrile to afford the target epothilone A.
| 【1】 Hindupur, R.M.; et al.; Total synthesis of epothilone A. Tetrahedron Lett 2001, 42, 42, 7341. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXI) | 52612 | 3,7,16-tris{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-15-hydroxy-4,4,6,8-tetramethyl-5-oxo-12-heptadecenoic acid | C39H80O7Si3 | 详情 | 详情 | |
| (XXII) | 52611 | 4,8-bis{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-16-(1-hydroxyethyl)-5,5,7,9-tetramethyloxa-13-cyclohexadecene-2,6-dione | C33H64O6Si2 | 详情 | 详情 | |
| (XXIII) | 52613 | 16-acetyl-4,8-bis{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-5,5,7,9-tetramethyloxa-13-cyclohexadecene-2,6-dione | C33H62O6Si2 | 详情 | 详情 | |
| (XXIV) | 52614 | dimethyl (2-methyl-1,3-thiazol-4-yl)methylphosphonate | C7H12NO3PS | 详情 | 详情 | |
| (XXV) | 44446 | (4S,7R,8S,9S,16S)-4,8-bis[[tert-butyl(dimethyl)silyl]oxy]-5,5,7,9-tetramethyl-16-[(E)-1-methyl-2-(2-methyl-1,3-thiazol-4-yl)ethenyl]oxa-13-cyclohexadecene-2,6-dione | C38H67NO5SSi2 | 详情 | 详情 | |
| (XXVI) | 44447 | (4S,7R,8S,9S,16S)-4,8-dihydroxy-5,5,7,9-tetramethyl-16-[(E)-1-methyl-2-(2-methyl-1,3-thiazol-4-yl)ethenyl]oxa-13-cyclohexadecene-2,6-dione | C26H39NO5S | 详情 | 详情 |