【结 构 式】 |
【分子编号】47617 【品名】 【CA登记号】 |
【 分 子 式 】C41H78O4Si3 【 分 子 量 】719.32442 【元素组成】C 68.46% H 10.93% O 8.9% Si 11.71% |
合成路线1
该中间体在本合成路线中的序号:(X)Oxidation of hydroxylated diene (I) with m-CPBA followed by acetylation provides epoxide (II), which is then converted to the corresponding hydroxy derivative (III) by means of SeO2 and PyO in dioxane followed by isomer separation. Treatment of compound (III) with t-butyldimethylsilyl chloride and imidazole in DMF yields the 5,7-bis-protected derivative (IV), which reacts in THF with tungsten hexachloride (WCl6) and BuLi in hexane/THF to furnish compound (V). Hydrolysis of acetate (V) with NaOH in MeOH provides alcohol (VI), which is then converted into the corresponding chloro derivative (VII) by treatment with N-chlorosuccinimide (NCS) and dimethylsulfide (Me2S) in CH2Cl2. Treatment of compound (VII) with potassium diphenylphosphide (PPh2K) in THF and aqueous H2O2 in CH2Cl2 gives diphenylphosphine oxide (VIII), which is condensed in THF with hexahydro indenone derivative (IX) by means of n-BuLi in hexane to afford compound (X). Finally, derivative (X) is deprotected by treatment with tetrabutyl ammonium fluoride in THF to yield the desired product.
【1】 Kiegiel, J.; et al.; Chemical conversion of vitamin D3 to its 1,25-dihydroxy metabolite. Tetrahedron Lett 1991, 32, 43, 6057. |
【2】 Batcho, A.D.; Hennessy, B.M.; Uskokovic, M.R. (F. Hoffmann-La Roche AG); Vitamin D3 analogs. WO 0104089 . |
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) | 47609 | 2-((5S)-5-[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)-1-ethanol | C15H28O2Si | 详情 | 详情 | |
(II) | 47610 | ((2R,3S,7S)-7-[[tert-butyl(dimethyl)silyl]oxy]-4-methylene-1-oxaspiro[2.5]oct-2-yl)methyl acetate | C17H30O4Si | 详情 | 详情 | |
(III) | 47611 | ((2R,3S,5S,7S)-7-[[tert-butyl(dimethyl)silyl]oxy]-5-hydroxy-4-methylene-1-oxaspiro[2.5]oct-2-yl)methyl acetate | C17H30O5Si | 详情 | 详情 | |
(IV) | 47612 | ((2R,3S,5S,7S)-5,7-bis[[tert-butyl(dimethyl)silyl]oxy]-4-methylene-1-oxaspiro[2.5]oct-2-yl)methyl acetate | C23H44O5Si2 | 详情 | 详情 | |
(V) | 47613 | 2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethyl acetate | C23H44O4Si2 | 详情 | 详情 | |
(VI) | 47614 | 2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)-1-ethanol | C21H42O3Si2 | 详情 | 详情 | |
(VII) | 47615 | tert-butyl(dimethyl)silyl (1R,3S)-3-[[tert-butyl(dimethyl)silyl]oxy]-5-[(E)-2-chloroethylidene]-4-methylenecyclohexyl ether; tert-butyl([(1R,3S)-3-[[tert-butyl(dimethyl)silyl]oxy]-5-[(E)-2-chloroethylidene]-4-methylenecyclohexyl]oxy)dimethylsilane | C21H41ClO2Si2 | 详情 | 详情 | |
(VIII) | 42574 | [2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethyl](oxo)diphenylphosphorane; 2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethyl(diphenyl)phosphine oxide | C33H51O3PSi2 | 详情 | 详情 | |
(IX) | 47616 | (3aR,7aS)-1-[(1R)-1,5-dimethyl-5-[(trimethylsilyl)oxy]hexyl]-7a-methyl-3,3a,5,6,7,7a-hexahydro-4H-inden-4-one | C21H38O2Si | 详情 | 详情 | |
(X) | 47617 | C41H78O4Si3 | 详情 | 详情 |