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【结 构 式】 
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【分子编号】58003 【品名】(1R,2R)-2-(benzyloxy)-1-vinyl-3-butenyl acetate 【CA登记号】 |
【 分 子 式 】C15H18O3 【 分 子 量 】246.30612 【元素组成】C 73.15% H 7.37% O 19.49% |
合成路线1
该中间体在本合成路线中的序号：(VII)Diisopropylidene mannitol (I) was first converted into the dibutyltin derivative (II), which was subsequently mono-benzylated to (III). Acetylation of (III) with acetic anhydride in pyridine gave (IV). After acidic hydrolysis of the isopropylidene ketals of (IV), the resultant tetraol (V) was converted into tetramesylate (VI). Reductive elimination in (VI) with Zn and NaI produced diene (VII). The acetate group of (VII) was then hydrolyzed to (VIII) using NaOMe. Intermediate (VIII) was reacted with triethyl orthoacetate in the presence of propionic acid to generate the allyl vinyl ether (IX), which underwent a Claisen rearrangement to the diene-ester (X). Selective hydroboration-oxidation of the terminal double bond of (X) yielded the primary alcohol (XI). Subsequent benzyl group hydrogenolysis in (XI) furnished the target intermediate diol (XII).
| 【1】 Rao, A.V.R.; et al.; Synthesis of (3R,4R)-1,5-hexadien-3,4-diol and its unsymmetrical derivatives: Application to (R)-(+)-alpha-lipoic acid. Tetrahedron Lett 1987, 28, 19, 2183. |
| 【2】 Yadav, J.S.; et al.; Synthesis of (3R,4R)-1,2-divinylglycol and its unsymmetrical derivatives: An application to the synthesis of R-(+)-alpha lipoic acid. J Carbohydr Chem 1990, 9, 2-3, 307. |
| 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) | 45944 | (1S,2S)-1,2-bis[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-1,2-ethanediol | 1707-77-3 | C12H22O6 | 详情 | 详情 |
| (II) | 57998 | (4R,5R)-2,2-dibutoxy-4,5-bis[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-1,3,2-dioxastannolane | C20H38O8Sn | 详情 | 详情 | |
| (III) | 57999 | (1S,2S)-2-(benzyloxy)-1,2-bis[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-ethanol | C19H28O6 | 详情 | 详情 | |
| (IV) | 58000 | (1S,2R)-2-(benzyloxy)-1,2-bis[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]ethyl acetate | C21H30O7 | 详情 | 详情 | |
| (V) | 58001 | (1R,2R,3R)-2-(benzyloxy)-1-[(1R)-1,2-dihydroxyethyl]-3,4-dihydroxybutyl acetate | C15H22O7 | 详情 | 详情 | |
| (VI) | 58002 | (1S,2S,3R)-2-(benzyloxy)-1-{(1R)-1,2-bis[(methylsulfonyl)oxy]ethyl}-3,4-bis[(methylsulfonyl)oxy]butyl acetate | C19H30O15S4 | 详情 | 详情 | |
| (VII) | 58003 | (1R,2R)-2-(benzyloxy)-1-vinyl-3-butenyl acetate | C15H18O3 | 详情 | 详情 | |
| (VIII) | 58004 | (3R,4R)-4-(benzyloxy)-1,5-hexadien-3-ol | C13H16O2 | 详情 | 详情 | |
| (IX) | 58005 | 1-[({(1R,2R)-2-[(1-ethoxyvinyl)oxy]-1-vinyl-3-butenyl}oxy)methyl]benzene; benzyl (1R,2R)-2-[(1-ethoxyvinyl)oxy]-1-vinyl-3-butenyl ether | C17H22O3 | 详情 | 详情 | |
| (X) | 58006 | ethyl (4E,6R)-6-(benzyloxy)-4,7-octadienoate | C17H22O3 | 详情 | 详情 | |
| (XI) | 58007 | ethyl (E,6R)-6-(benzyloxy)-8-hydroxy-4-octenoate | C17H24O4 | 详情 | 详情 | |
| (XII) | 57958 | ethyl (6S)-6,8-dihydroxyoctanoate | C10H20O4 | 详情 | 详情 |