|
【结 构 式】 
|
【分子编号】29880 【品名】methyl (2E)-2,4-pentadienoate 【CA登记号】 |
【 分 子 式 】C6H8O2 【 分 子 量 】112.12832 【元素组成】C 64.27% H 7.19% O 28.54% |
合成路线1
该中间体在本合成路线中的序号：(V)(ii) The asymmetric construction of the hydroxymercaptoheptenoic acid: For construction of the hydroxymercaptoheptenoic acid (VIII), cesium triphenylmethylthiolate anion was added to methyl 2,4-pentadienoate (V), which resulted in a beta,gamma-unsaturated methyl ester that was converted to an alpha,beta-unsaturated ester after exposure to Cs2CO3. DIBAL reduction to the primary alcohol followed by Swern oxidation yielded the alpha,beta-unsaturated aldehyde (VI). In the presence of the ligand derived from (R)-(-)-binaphthyl amino alcohol, Ti(IV)-catalyzed addition of O-benzyl, O-TMS ketene acetal to the alpha,beta-unsaturated aldehyde (VI) resulted in the aldol product (VII). Hydrolysis of the benzyl ester with LiOH in aqueous methanol formed the beta-hydroxymercaptoheptenoic acid (VIII).
| 【1】 Li, K.W.; Simon, J.A.; Xing, W.; Wu, J.; Total synthesis of the antitumor depsipeptide FR901228. J Am Chem Soc 1996, 118, 30, 7237. |
| 【2】 Wang, H.-C. R.; FR901228. Drugs Fut 1999, 24, 11, 1184. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 29882 | [[1-(benzyloxy)vinyl]oxy](trimethyl)silane; benzyl 1-[(trimethylsilyl)oxy]vinyl ether | C12H18O2Si | 详情 | 详情 | ||
| (V) | 29880 | methyl (2E)-2,4-pentadienoate | C6H8O2 | 详情 | 详情 | |
| (VI) | 29881 | (E)-5-(tritylsulfanyl)-2-pentenoic acid | C24H22O2S | 详情 | 详情 | |
| (VII) | 29883 | benzyl (3R,4E)-3-hydroxy-7-(tritylsulfanyl)-4-heptenoate | C33H32O3S | 详情 | 详情 | |
| (VIII) | 29884 | (3R,4E)-3-hydroxy-7-(tritylsulfanyl)-4-heptenoic acid | C26H26O3S | 详情 | 详情 |