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【结 构 式】 
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【分子编号】60154 【品名】(3S,8R,9S,10R,13S,14S,16R)-3-{[tert-butyl(dimethyl)silyl]oxy}-17-[(E)ethylidene]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-16-ol 【CA登记号】 |
【 分 子 式 】C27H46O2Si 【 分 子 量 】430.74654 【元素组成】C 75.29% H 10.76% O 7.43% Si 6.52% |
合成路线1
该中间体在本合成路线中的序号：(XXIX)Synthesis of the target cholestane glycoside. The reaction of 3-beta-hydroxy-5-androsten-17-one (XXV) with Tbdms-Cl gives the silyl ether (XXVI), which is condensed with phosphorane (XXVII), yielding the ethylidene derivative (XXVIII). The oxidation of (XXVIII) by means of SeO2 and tert-butyl hydroperoxide affords the alcohol (XXIX), which is submitted to a Swern oxidation to provide the enone (XXX). The condensation of (XXX) with the intermediate vinyl bromide (XXIV) by means of CuCN, LiCl and Tms-Cl gives the non isolated intermediate (XXXI), which is treated with acetyl chloride to yield the enol acetate (XXXII). The reaction of (XXXII) with ethyleneglycol and PPTS in dichloromethane affords the ethylene ketal (XXXIII), which is submitted to a stereoselective oxidation with Davis reagent and t-BuOK to provide the hydroxy ketone (XXXIV). The stereoselective reduction of (XXXIV) by means of LiAlH4 in dichloromethane leads to the dihydroxy compound (XXXV).
| 【1】 Yu, W.; Jin, Z.; Total synthesis of the anticancer natural product OSW-1. J Am Chem Soc 2002, 124, 23, 6576. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (A) | 11295 | Polyethylene glycol;1,2-Ethanediol;Monoethylene glycol; Ethylene glycol | 107-21-1 | C2H6O2 | 详情 | 详情 |
| (XXIV) | 48956 | (E)-1-bromo-4-methyl-1-pentenyl cyclohexyl ether; 1-[[(E)-1-bromo-4-methyl-1-pentenyl]oxy]cyclohexane | C12H21BrO | 详情 | 详情 | |
| (XXV) | 11713 | Dehydroepiandrosterone;prasterone；(3S,8R,9S,10R,13S,14S)-3-Hydroxy-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-17-one | 53-43-0 | C19H28O2 | 详情 | 详情 |
| (XXVI) | 16818 | (3S,8R,9S,10R,13S,14S)-3-[[tert-butyl(dimethyl)silyl]oxy]-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-17-one | C25H42O2Si | 详情 | 详情 | |
| (XXVII) | 60152 | ethylidene(triphenyl)phosphorane | C20H19P | 详情 | 详情 | |
| (XXVIII) | 60153 | tert-butyl(dimethyl)silyl (3S,8S,9S,10R,13S,14S)-17-[(Z)ethylidene]-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-3-yl ether; tert-butyl({(3S,8S,9S,10R,13S,14S)-17-[(Z)ethylidene]-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-3-yl}oxy)dimethylsilane | C27H46OSi | 详情 | 详情 | |
| (XXIX) | 60154 | (3S,8R,9S,10R,13S,14S,16R)-3-{[tert-butyl(dimethyl)silyl]oxy}-17-[(E)ethylidene]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-16-ol | C27H46O2Si | 详情 | 详情 | |
| (XXX) | 60155 | (3S,8R,9S,10R,13S,14S)-3-{[tert-butyl(dimethyl)silyl]oxy}-17-[(E)ethylidene]-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,17-tetradecahydro-16H-cyclopenta[a]phenanthren-16-one | C27H44O2Si | 详情 | 详情 | |
| (XXXI) | 60156 | tert-butyl(dimethyl)silyl (3S,8R,9S,10R,13S,14S)-17-[(1S,2Z)-2-(cyclohexyloxy)-1,5-dimethyl-2-hexenyl]-10,13-dimethyl-16-[(trimethylsilyl)oxy]-2,3,4,7,8,9,10,11,12,13,14,15-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl ether; tert-butyl({(3S,8R,9S,10R,13S,14S)-17-[(1S,2Z)-2-(cyclohexyloxy)-1,5-dimethyl-2-hexenyl]-10,13-dimethyl-16-[(trimethylsilyl)oxy]-2,3,4,7,8,9,10,11,12,13,14,15-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl}oxy)dimethylsilane | C42H74O3Si2 | 详情 | 详情 | |
| (XXXII) | 60157 | (3S,8R,9S,10R,13S,14S)-3-{[tert-butyl(dimethyl)silyl]oxy}-17-[(1S,2Z)-2-(cyclohexyloxy)-1,5-dimethyl-2-hexenyl]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15-dodecahydro-1H-cyclopenta[a]phenanthren-16-yl acetate | C41H68O4Si | 详情 | 详情 | |
| (XXXIII) | 60158 | (3S,8R,9S,10R,13S,14S)-3-{[tert-butyl(dimethyl)silyl]oxy}-17-[(1S)-1-(2-isopentyl-1,3-dioxolan-2-yl)ethyl]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15-dodecahydro-1H-cyclopenta[a]phenanthren-16-yl acetate | C37H62O5Si | 详情 | 详情 | |
| (XXXIV) | 60159 | (3S,8R,9S,10R,13S,14S,17S)-3-{[tert-butyl(dimethyl)silyl]oxy}-17-hydroxy-17-[(1S)-1-(2-isopentyl-1,3-dioxolan-2-yl)ethyl]-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,17-tetradecahydro-16H-cyclopenta[a]phenanthren-16-one | C35H60O5Si | 详情 | 详情 | |
| (XXXV) | 60160 | (3S,8R,9S,10R,13S,14S,16S,17S)-3-{[tert-butyl(dimethyl)silyl]oxy}-17-[(1S)-1-(2-isopentyl-1,3-dioxolan-2-yl)ethyl]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene-16,17-diol | C35H62O5Si | 详情 | 详情 |