【结 构 式】 |
【分子编号】47728 【品名】(5S)-5-[(1S,3aS,7aS)-4-[(E)-2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethylidene]-7a-methyloctahydro-4H-inden-1-yl]-1,1-dimethylhexyl triethylsilyl ether; [((1R,5S)-3-[(Z)-2-((1S,3aS,7aS)-1-[(1S)-1,5-dimethyl-5-[(triethylsilyl)oxy]hexyl]-7a-methyloctahydro-4H-inden-4-ylidene)ethylidene]-5-[[tert-butyl(dimethyl)silyl]oxy]-4-methylenecyclohexyl)oxy](tert-butyl)dimethylsilane 【CA登记号】 |
【 分 子 式 】C45H86O3Si3 【 分 子 量 】759.43254 【元素组成】C 71.17% H 11.41% O 6.32% Si 11.09% |
合成路线1
该中间体在本合成路线中的序号:(XIX)The oxidation of the ring A precursor alcohol (XIV) with Dess-Martin reagent gave rise to a mixture of aldehyde (XV) and its cyclic tautomer, the pyran derivative (XVI). Coupling of this mixture with the lithium anion of sulfone (XIII), followed by quenching with acetyl chloride, furnished the target beta-acetoxy sulfone adduct (XVII) accompanied by the silyl-acetyl exchange product (XVIII). Reductive cleavage of the phenylsulfonyl group by means of sodium amalgam yielded the desired O-triethylsilyl triene (XIX) along with some O-acetyl byproduct. Finally, desilylation of (XIX) with tetrabutylammonium fluoride provided the title triol derivative, which was separated from its C-25 acetate byproduct by flash chromatography.
【1】 Marczak, S.; et al.; Synthesis and biological activity of the 1alpha,25-dihydroxyvitamin D3 diastereomer with unnatural configuration at the rings C/D side-chain moiety. Bioorg Med Chem Lett 2001, 11, 1, 63. |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
(XIII) | 47723 | (1S,3aS,4S,7aS)-1-[(1S)-1,5-dimethyl-5-[(triethylsilyl)oxy]hexyl]-7a-methyloctahydro-1H-inden-4-yl phenyl sulfone; ([(5S)-5-[(1S,3aS,4S,7aS)-7a-methyl-4-(phenylsulfonyl)octahydro-1H-inden-1-yl]-1,1-dimethylhexyl]oxy)(triethyl)silane | C30H52O3SSi | 详情 | 详情 | |
(XIV) | 47614 | 2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)-1-ethanol | C21H42O3Si2 | 详情 | 详情 | |
(XV) | 47724 | 2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)acetaldehyde | C21H40O3Si2 | 详情 | 详情 | |
(XVI) | 47725 | tert-butyl(dimethyl)silyl (6R,8S)-6-[[tert-butyl(dimethyl)silyl]oxy]-5,6,7,8-tetrahydro-1H-isochromen-8-yl ether; tert-butyl[((6R,8S)-8-[[tert-butyl(dimethyl)silyl]oxy]-5,6,7,8-tetrahydro-1H-isochromen-6-yl)oxy]dimethylsilane | C21H40O3Si2 | 详情 | 详情 | |
(XVII) | 47726 | 1-[(1S,3aS,7aS)-1-[(1S)-1,5-dimethyl-5-[(triethylsilyl)oxy]hexyl]-7a-methyl-4-(phenylsulfonyl)octahydro-1H-inden-4-yl]-2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethyl acetate | C53H94O7SSi3 | 详情 | 详情 | |
(XVIII) | 47727 | (5S)-5-[(1S,3aS,7aS)-4-[1-(acetoxy)-2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethyl]-7a-methyl-4-(phenylsulfonyl)octahydro-1H-inden-1-yl]-1,1-dimethylhexyl acetate | C49H82O8SSi2 | 详情 | 详情 | |
(XIX) | 47728 | (5S)-5-[(1S,3aS,7aS)-4-[(E)-2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethylidene]-7a-methyloctahydro-4H-inden-1-yl]-1,1-dimethylhexyl triethylsilyl ether; [((1R,5S)-3-[(Z)-2-((1S,3aS,7aS)-1-[(1S)-1,5-dimethyl-5-[(triethylsilyl)oxy]hexyl]-7a-methyloctahydro-4H-inden-4-ylidene)ethylidene]-5-[[tert-butyl(dimethyl)silyl]oxy]-4-methylenecyclohexyl)oxy](tert-butyl)dimethylsilane | C45H86O3Si3 | 详情 | 详情 |