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【结 构 式】 
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【分子编号】29327 【品名】[(E)-2-butyl-5-(tributylstannyl)-2-vinyl-4-pentenyl](trimethyl)silane 【CA登记号】 |
【 分 子 式 】C26H54SiSn 【 分 子 量 】513.51026 【元素组成】C 60.81% H 10.6% Si 5.47% Sn 23.12% |
合成路线1
该中间体在本合成路线中的序号：(XVI)The oxidation of 1-hepten-3-ol (XI) with pyridinium chlorochromate gives 1-hepten-3-one (XIII), which by a Grignard condensation with propargylmagnesium bromide (XIII) is converted to 4-hydroxy-4-vinyl-1-octyne (XIV). The protection of (XIV) with trimethylsilyl chloride and imidazole as before yields 4-trimethylsilyloxy-4-vinyl-1-octyne (XV), which by reaction with tri-n-butylstannane and azobisisobutyronitrile at 125 C affords 1-(tri-n-butylstannyl)-4-vinyl-4-(trimethylsilyloxy)-1-octene (XVI). Finally, this compound, by reaction with butyllithium and copper(I)-1-pentyne tributylphosphine as before yields the copper salt (VIII), which is condensed with 2-(6-trimethylsilyloxycarbonyl)-2-cis-hexenyl)-4-trime-thylsilyloxycyclopent-2-en-1-one (IX) in ether-THF giving trimethylsilyl-9-oxo-11 alpha,16-bis(trimethylsilyloxy)-16-vinyl-5-cis-13-trans-prostadienoate (X). Finally, this compound is hydrolyzed with acetic acid in THF water.
| 【1】 Grudzinkas, C.V.; Bimbaum, J.E.; Chen. S.L.; Chan, P.S.; Floyd, M.B.; Weiss, M.J.; Cervoni, P.; Prostaglandins and congeners. 29. (16RS)-Rac-15-deoxy-16-hydroxy-16-vivyl-protaglandin E2, an orally and transdermally active hypotensive agent of prolonged duration. J Med Chem 1982, 25, 5, 492-494. |
| 【2】 Adaikan, P.G.; Serradell, M.N.; Castaner, J.; DHV-PGE2. Drugs Fut 1985, 10, 5, 382. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (B) | 29319 | 1-Pentynyl copper salt tri(tert-butyl)phosphine complex | C17H34CuP | 详情 | 详情 | |
| (VIII) | 29320 | [(1E)-4-butyl-4-[(trimethylsilyl)methyl]-1,5-hexadienyl](1-pentynyl)copper | C19H34CuSi | 详情 | 详情 | |
| (IX) | 29321 | (4R)-2-[(Z)-7-oxo-8-(trimethylsilyl)-2-octenyl]-4-[(trimethylsilyl)methyl]-2-cyclopenten-1-one | C20H36O2Si2 | 详情 | 详情 | |
| (X) | 29322 | (2R,3R,4R)-3-[(1E)-4-butyl-4-[(trimethylsilyl)methyl]-1,5-hexadienyl]-2-[(Z)-7-oxo-8-(trimethylsilyl)-2-octenyl]-4-[(trimethylsilyl)methyl]cyclopentanone | C34H64O2Si3 | 详情 | 详情 | |
| (XI) | 29323 | 1-hexen-3-ol | 4798-44-1 | C6H12O | 详情 | 详情 |
| (XII) | 29324 | 1-hexen-3-one | 1629-60-3 | C6H10O | 详情 | 详情 |
| (XIII) | 29064 | bromo(2-propynyl)magnesium | C3H3BrMg | 详情 | 详情 | |
| (XIV) | 29325 | 3-butyl-1-hexen-5-yn-3-ol | C10H16O | 详情 | 详情 | |
| (XV) | 29326 | (2-butyl-2-vinyl-4-pentynyl)(trimethyl)silane | C14H26Si | 详情 | 详情 | |
| (XVI) | 29327 | [(E)-2-butyl-5-(tributylstannyl)-2-vinyl-4-pentenyl](trimethyl)silane | C26H54SiSn | 详情 | 详情 |