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【结 构 式】 
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【分子编号】34604 【品名】(1S,5R)-3-((Z)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-5-[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexanol 【CA登记号】 |
【 分 子 式 】C34H58O2Si 【 分 子 量 】526.91882 【元素组成】C 77.5% H 11.09% O 6.07% Si 5.33% |
合成路线1
该中间体在本合成路线中的序号：(XXVII)The silylation of vitamin D2 (XXIII) with TBDMS-Cl and imidazole in dichloromethane gives the silyl ether (XXIV), which is cyclized with N-sulfinyl-p-toluenesulfonamide yielding the Diels-Alder adduct (XXV). The oxidation of (XXV) with SeO2 and N-methylmorpholine-oxide in ethanol affords the trans-1alpha-hydroxy-3-O-(tert-butyldimethylsilyl)vitamin D2 (XXVI), which is irradiated with UV light in benzene containing anthracene yielding 1alpha-hydroxy-3-O-(tert-butyldimethylsilyl)vitamin D2 (XXVII). Finally, this compound is desilylated with TBAF in THF. The cyclization of the silyl ether (XXIV) can also be performed with Ts-N=Se=N-Ts yielding the corresponding adduct (XXVIII), which is oxidized with SeO2 as before to afford the trans-1alpha-hydroxy-3-O-(tert-butyldimethylsilyl) vitamin D2 (XXVI) already reported.
| 【1】 Guo, L.; Moriarty, R.M.; Penmasta, R.A. (Lunar Corp.); Synthesis of 1alpha-hydroxy vitamin D. WO 9602501 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXIII) | 12425 | (1S)-3-((Z)-2-[(1R,3aR,7aR)-7a-Methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexanol | 50-14-6 | C28H44O | 详情 | 详情 |
| (XXIV) | 34603 | [[(1S)-3-((Z)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexyl]oxy](tert-butyl)dimethylsilane; (1S)-3-((Z)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexyl tert-butyl(dimethyl)silyl ether | C34H58OSi | 详情 | 详情 | |
| (XXV) | 34600 | (5S)-4-([(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]methyl)-5-[[tert-butyl(dimethyl)silyl]methyl]-3-[(4-methylphenyl)sulfonyl]-3,4,5,6,7,8-hexahydro-2lambda(4),3-benzothiazin-2(1H)-one | C42H67NO3S2Si | 详情 | 详情 | |
| (XXVI) | 34601 | (1S,5R)-3-((E)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-5-[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexanol | C34H58O2Si | 详情 | 详情 | |
| (XXVII) | 34604 | (1S,5R)-3-((Z)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-5-[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexanol | C34H58O2Si | 详情 | 详情 | |
| (XXVIII) | 34599 | N-[(5S)-4-([(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]methyl)-5-[[tert-butyl(dimethyl)silyl]methyl]-3-[(4-methylphenyl)sulfonyl]-3,4,5,6,7,8-hexahydro-2lambda(4),3-benzoselenazin-2(1H)-ylidene]-4-met | C49H74N2O4S2SeSi | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XXVII)
| 【1】 Andrews DR, Barton DHR, et aL. 1986.A direct, regio- and stereoselective lα-rhydroxylation of (5E-calciferol derivatives.J Org Chem, 51: 1635~1637 |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXIII) | 12425 | (1S)-3-((Z)-2-[(1R,3aR,7aR)-7a-Methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexanol | 50-14-6 | C28H44O | 详情 | 详情 |
| (XXVI) | 34601 | (1S,5R)-3-((E)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-5-[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexanol | C34H58O2Si | 详情 | 详情 | |
| (XXVII) | 34604 | (1S,5R)-3-((Z)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-5-[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexanol | C34H58O2Si | 详情 | 详情 | |
| (XXIX) | 34605 | (1S)-3-((E)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexanol | C28H44O | 详情 | 详情 | |
| (XXXI) | 12428 | (1S)-3-((E)-2-[(1R,3aR,7aR)-7a-Methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexyl tert-butyl(dimethyl)silyl ether; [[(1S)-3-((E)-2-[(1R,3aR,7aR)-7a-Methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexyl]oxy](tert-butyl)dimethylsilane | C34H58OSi | 详情 | 详情 |