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【结 构 式】 
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【分子编号】31274 【品名】5-[(2R)-2-[(1S,8S,9S,10R,13R,14S,17R)-1,3-dihydroxy-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl]propyl]-3-hydroxy-3-methyldihydro-2(3H)-furanone 【CA登记号】 |
【 分 子 式 】C27H42O5 【 分 子 量 】446.62748 【元素组成】C 72.61% H 9.48% O 17.91% |
合成路线1
该中间体在本合成路线中的序号：(IVc)The less polar major isomer (IVa) was reduced to lactone (IVb) with 10 eq of tri-n-butyltin hydride (tetrahydrofuran, room temperature, 4 h) in 88% yield. Treatment of the lactone (IVb) with a catalytic amount of HCl in methanol at 50 C for 5 h gave the diol (IVc) in 88% yield. Reaction of (IVc) with ethyl chloroformate (16 eq) in the presence of 4-dimethylaminopyridine (17 eq) at room temperature for 15 h afforded ethyl carbonate (IVd) in 82% yield. Allylic bromination of (IVd) with 0.6 eq of 1,3-dibromo-5,5-dimethylhydantoin in n-hexane under reflux followed by dehydrobromination with collidine in refluxing xylene gave the 5,7-diene (V) as the major product. Alkaline hydrolysis (KOH, methanol, room temperature, 15 h) and purification by preparative thin-layer chromatography (TLC) gave the 5,7-diene in 53% yield from (IVd).
| 【1】 Morris, D.S.; Norris, A.F.; Williams, D.H.; Structure and synthesis of 25-hydroxycholecalciferol-26,23-lactone, a metabolite of vitamin D3. J Org Chem 1981, 46, 3422-28. |
| 【2】 Seino, Y.; Ishizuka, S.; 23(S),25(R)-1alpha,25-(OH)2-D3-26,23-Lactone. Drugs Fut 1992, 17, 8, 655. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (IVa) | 31272 | 5-[(2S)-2-[(1S,8S,9S,10R,13S,14S,17R)-1,3-bis(methoxymethoxy)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl]-1-iodopropyl]-3-hydroxy-3-methyldihydro-2(3H)-furanone | C31H49IO7 | 详情 | 详情 | |
| (IVb) | 31273 | 5-[(2R)-2-[(1S,8S,9S,10R,13R,14S,17R)-1,3-bis(methoxymethoxy)-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl]propyl]-3-hydroxy-3-methyldihydro-2(3H)-furanone | C31H50O7 | 详情 | 详情 | |
| (IVc) | 31274 | 5-[(2R)-2-[(1S,8S,9S,10R,13R,14S,17R)-1,3-dihydroxy-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl]propyl]-3-hydroxy-3-methyldihydro-2(3H)-furanone | C27H42O5 | 详情 | 详情 | |
| (F) | 31275 | N,N-dimethyl-N-(4-pyridinyl)amine; N,N-dimethyl-4-pyridinamine | 1122-58-3 | C7H10N2 | 详情 | 详情 |
| (IVd) | 31276 | (1S,8S,9S,10R,13R,14S,17R)-1-[(ethoxycarbonyl)oxy]-17-[(1R)-2-(4-hydroxy-4-methyl-5-oxotetrahydro-2-furanyl)-1-methylethyl]-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl ethyl carbonate | C33H50O9 | 详情 | 详情 | |
| (G) | 31277 | 1,3-dibromo-5,5-dimethyl-2,4-imidazolidinedione | 77-48-5 | C5H6Br2N2O2 | 详情 | 详情 |
| (V) | 31278 | ethyl (1S,9S,10S,13R,14R,17R)-3-[(ethoxycarbonyl)oxy]-17-[(1R)-2-(4-hydroxy-4-methyl-5-oxotetrahydro-2-furanyl)-1-methylethyl]-10,13-dimethyl-2,3,4,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthrene-1-carboxylate | C33H48O8 | 详情 | 详情 |