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【结 构 式】 
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【分子编号】46198 【品名】(1S,3S,7S,10R,11S,12S,16R)-7,11-bis[[tert-butyl(dimethyl)silyl]oxy]-8,8,10,12,16-pentamethyl-3-[(E)-1-methyl-2-(2-methyl-1,3-thiazol-4-yl)ethenyl]-4,17-dioxabicyclo[14.1.0]heptadecane-5,9-dione 【CA登记号】 |
【 分 子 式 】C39H69NO6SSi2 【 分 子 量 】736.217 【元素组成】C 63.63% H 9.45% N 1.9% O 13.04% S 4.36% Si 7.63% |
合成路线1
该中间体在本合成路线中的序号：(XLIV)The treatment of (XXXIX) with Tbdms-OTf as before gives the silyl ether (XL), which is oxidized at its terminal double bond with OsO4 and NaIO4 to give the aldehyde (XLI).The oxidation of (XLI) with NaClO2 yields the carboxylic acid (XLII), which is selectively deprotected with TBAF in THF affording the hydroxyacid (XLIII). The macrolactonization of (XLIII) by means of 2,3,6-trichlorobenzoyl chloride and TEA in toluene provides the protected macrolactone (XLIV), which is finally desilylated by means of TFA in dichloromethane to yield the target epothilone B.
| 【1】 Mulzer, J.; et al.; A novel highly stereoselective total synthesis of epothilone B and of its (12R,13R) acetonide. Tetrahedron Lett 2000, 41, 40, 7635. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXXIX) | 46193 | (4S,7R,8S,9S)-4-[[tert-butyl(dimethyl)silyl]oxy]-12-[(2R,3S)-3-[(2S,3E)-2-[[tert-butyl(dimethyl)silyl]oxy]-3-methyl-4-(2-methyl-1,3-thiazol-4-yl)-3-butenyl]-2-methyloxiranyl]-8-hydroxy-5,5,7,9-tetramethyl-1-dodecen-6-one | C40H73NO5SSi2 | 详情 | 详情 | |
| (XL) | 46194 | (5S,8R,9S)-5-allyl-9-((1S)-4-[(2R,3S)-3-[(2S,3E)-2-[[tert-butyl(dimethyl)silyl]oxy]-3-methyl-4-(2-methyl-1,3-thiazol-4-yl)-3-butenyl]-2-methyloxiranyl]-1-methylbutyl)-2,2,3,3,6,6,8,11,11,12,12-undecamethyl-4,10-dioxa-3,11-disilatridecan-7-one | C46H87NO5SSi3 | 详情 | 详情 | |
| (XLI) | 46195 | (3S,6R,7S,8S)-3,7-bis[[tert-butyl(dimethyl)silyl]oxy]-11-[(2R,3S)-3-[(2S,3E)-2-[[tert-butyl(dimethyl)silyl]oxy]-3-methyl-4-(2-methyl-1,3-thiazol-4-yl)-3-butenyl]-2-methyloxiranyl]-4,4,6,8-tetramethyl-5-oxoundecanal | C45H85NO6SSi3 | 详情 | 详情 | |
| (XLII) | 46196 | (3S,6R,7S,8S)-3,7-bis[[tert-butyl(dimethyl)silyl]oxy]-11-[(2R,3S)-3-[(2S,3E)-2-[[tert-butyl(dimethyl)silyl]oxy]-3-methyl-4-(2-methyl-1,3-thiazol-4-yl)-3-butenyl]-2-methyloxiranyl]-4,4,6,8-tetramethyl-5-oxoundecanoic acid | C45H85NO7SSi3 | 详情 | 详情 | |
| (XLIII) | 46197 | (3S,6R,7S,8S)-3,7-bis[[tert-butyl(dimethyl)silyl]oxy]-11-[(2R,3S)-3-[(2S,3E)-2-hydroxy-3-methyl-4-(2-methyl-1,3-thiazol-4-yl)-3-butenyl]-2-methyloxiranyl]-4,4,6,8-tetramethyl-5-oxoundecanoic acid | C39H71NO7SSi2 | 详情 | 详情 | |
| (XLIV) | 46198 | (1S,3S,7S,10R,11S,12S,16R)-7,11-bis[[tert-butyl(dimethyl)silyl]oxy]-8,8,10,12,16-pentamethyl-3-[(E)-1-methyl-2-(2-methyl-1,3-thiazol-4-yl)ethenyl]-4,17-dioxabicyclo[14.1.0]heptadecane-5,9-dione | C39H69NO6SSi2 | 详情 | 详情 |