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【结 构 式】 
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【分子编号】34589 【品名】(1R,5S)-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-(acetoxy)-4-methylenecyclohexyl acetate 【CA登记号】 |
【 分 子 式 】C32H48O4 【 分 子 量 】496.73072 【元素组成】C 77.38% H 9.74% O 12.88% |
合成路线1
该中间体在本合成路线中的序号：(XIII)The reduction of (IX) with LiAlH4 in refluxing THF eliminates the Diels-Alder adduct and opens the 1alpha,2alpha-epoxide giving the 1alpha,2beta-diol (X), which is acylated with acetyl chloride in pyridine yielding the diacetoxy epoxide (XI). The reaction of (XI) with NaI and trifluoroacetic anhydride in acetonitrile/THF regenerates the 22,23-double bond affording 1alpha-acetoxyergosteryl acetate (XII), which is submitted to UV irradiation with a high pressure mercury lamp in ethyl ether to provide the diacetate of 1alpha-hydroxyvitamin D2 (XIII). Finally, this compound is deacylated with KOH in refluxing ethanol.
| 【1】 Tachibana, Y.; A convenient syntesis of a 1alpha-hydroxyvitamin D2. Bull Chem Soc Jpn 1988, 61, 11, 3915. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (IX) | 34585 | (1S,2R,5R,6R,10R,11R,13S,14R,16S)-5-((1S)-1-[3-[(1R)-1,2-dimethylpropyl]-2-oxiranyl]ethyl)-14-hydroxy-6,10-dimethyl-19-phenyl-12-oxa-17,19,21-triazaheptacyclo[14.5.2.0(1,9).0(2,6).0(10,16).0(11,13).0(17,21)]tricos-22-ene-18,20-dione | C36H47N3O5 | 详情 | 详情 | |
| (X) | 34586 | (1S,3R,10R,13R,14R,17R)-17-((1S)-1-[3-[(1R)-1,2-dimethylpropyl]-2-oxiranyl]ethyl)-10,13-dimethyl-2,3,4,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthrene-1,3-diol | C28H44O3 | 详情 | 详情 | |
| (XI) | 34587 | (1S,3R,10R,13R,14R,17R)-1-(acetoxy)-17-((1S)-1-[3-[(1R)-1,2-dimethylpropyl]-2-oxiranyl]ethyl)-10,13-dimethyl-2,3,4,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate | C32H48O5 | 详情 | 详情 | |
| (XII) | 34588 | (1S,3R,10R,13R,14R,17R)-1-(acetoxy)-10,13-dimethyl-17-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]-2,3,4,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate | C32H48O4 | 详情 | 详情 | |
| (XIII) | 34589 | (1R,5S)-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-(acetoxy)-4-methylenecyclohexyl acetate | C32H48O4 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XIII)The Oppenauer oxidation of ergosterol (XIX) gives ergosta-4,6,22-trien-3-one (I), which is dehydrogenated with SeO2 to ergosta-1,4,6,22-tetraen-3-one (II). The epoxidation of (II) with H2O2 and NaOH in dioxane affords the 1alpha,2alpha-epoxide (XX), which is reduced with Li in liquid NH3 to give ergost-5-ene-1alpha,3beta-diol (XXI). The acylation of (XXI) with acetic anhydride and pyridine yields the diacetate (XXII), which is dehydrogenated by the bromination dehydrobromination method to provide the previously reported 1alpha-acetoxyergosteryl acetate (XII). The UV irradiation of (XII) with a high pressure Hg lamp gives the 1alpha-hydroxyvitamin D2 diacetate (XIII), which is finally, deacylated with KOH in methanol.
| 【1】 Lam, H.Y.; et al.; Synthesis of 1alpha-hydroxyergocalciferol. Steroids 1977, 30, 5, 671. |
| 【2】 Schnoes, H.K.; DeLuca, H.F.; Lam, H.-Y. (Wisconsin Alumni Research Foundation); 1alpha-Hydroxyergocalciferol and processes for preparing same. US 3907843 . |
| 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) | 34578 | (10R,13R,14S,17R)-10,13-dimethyl-17-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]-1,2,8,9,10,11,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthren-3-one | C28H42O | 详情 | 详情 | |
| (II) | 34579 | (10S,13R,14S,17R)-10,13-dimethyl-17-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]-8,9,10,11,12,13,14,15,16,17-decahydro-3H-cyclopenta[a]phenanthren-3-one | C28H40O | 详情 | 详情 | |
| (XII) | 34588 | (1S,3R,10R,13R,14R,17R)-1-(acetoxy)-10,13-dimethyl-17-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]-2,3,4,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate | C32H48O4 | 详情 | 详情 | |
| (XIII) | 34589 | (1R,5S)-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-(acetoxy)-4-methylenecyclohexyl acetate | C32H48O4 | 详情 | 详情 | |
| (XIX) | 34595 | (3S,10R,13R,14R,17R)-10,13-dimethyl-17-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]-2,3,4,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-ol | 57-87-4 | C28H44O | 详情 | 详情 |
| (XX) | 34596 | (2aR,3aR,3bR,5aR,6R,8aS)-3b,5a-dimethyl-6-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]-2a,3a,3b,3c,4,5,5a,6,7,8,8a,8b-dodecahydro-2H-cyclopenta[7,8]phenanthro[3,4-b]oxiren-2-one | C28H40O2 | 详情 | 详情 | |
| (XXI) | 34597 | (1S,3R,10R,13R,14S,17R)-10,13-dimethyl-17-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene-1,3-diol | C28H46O2 | 详情 | 详情 | |
| (XXII) | 34598 | (1S,3R,10R,13R,14S,17R)-1-(acetoxy)-10,13-dimethyl-17-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate | C32H50O4 | 详情 | 详情 |