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【结 构 式】 
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【分子编号】47179 【品名】S-propyl (2S,3S,4E,6E,8S,9R,10S)-3-hydroxy-9-[(4-methoxybenzyl)oxy]-2,4,6,8,10-pentamethyl-4,6-icosadienethioate 【CA登记号】 |
【 分 子 式 】C36H60O4S 【 分 子 量 】588.936 【元素组成】C 73.42% H 10.27% O 10.87% S 5.44% |
合成路线1
该中间体在本合成路线中的序号：(XXV)The reduction of the ester group of (XIX) with DIBAL in dichloromethane gives the alcohol (XX), which is oxidized with TPAP and NMO in the same solvent, yielding the corresponding aldehyde (XXI). The condensation of (XXI) with phosphorane (XVIII) in refluxing THF affords the diunsaturated ester (XXII), which is reduced with DIBAL as before to provide the alcohol (XXIII). The oxidation of (XXIII) with TPAP and NMO as before gives the aldehyde (XXIV), which is condensed with the silyl enol ether (II) by means of Sn(OTf)2, Bu2Sn(OAc)2 and a chiral catalyst to yield the unsaturated thioester (XXV). The reaction of the OH group of (XXV) with Tes-OTf and lutidine in dichloromethane affords the silyl ether (XXVI), which is reduced with DIBAL in the same solvent to provide the corresponding aldehyde (XXVII).
| 【1】 Wakabayashi, T.; Mori, K.; Kobayashi, S.; Total synthesis and structural elucidation of khafrefungin. J Am Chem Soc 2001, 123, 7, 1372. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (II) | 47158 | (Z)-1-(propylsulfanyl)-1-propenyl trimethylsilyl ether; trimethyl[[(Z)-1-(propylsulfanyl)-1-propenyl]oxy]silane | C9H20OSSi | 详情 | 详情 | |
| (XI) | 47175 | (E,4S,5R,6S)-5-[(4-methoxybenzyl)oxy]-2,4,6-trimethyl-2-hexadecenal | C27H44O3 | 详情 | 详情 | |
| (XVIII) | 47172 | propyl 2-(triphenylphosphoranylidene)propanoate | C24H25O2P | 详情 | 详情 | |
| (XIX) | 47173 | propyl (E,4S,5R,6S)-5-[(4-methoxybenzyl)oxy]-2,4,6-trimethyl-2-hexadecenoate | C30H50O4 | 详情 | 详情 | |
| (XX) | 47174 | (E,4S,5R,6S)-5-[(4-methoxybenzyl)oxy]-2,4,6-trimethyl-2-hexadecen-1-ol | C27H46O3 | 详情 | 详情 | |
| (XXII) | 47176 | ethyl (2E,4E,6S,7R,8S)-7-[(4-methoxybenzyl)oxy]-2,4,6,8-tetramethyl-2,4-octadecadienoate | C32H52O4 | 详情 | 详情 | |
| (XXIII) | 47177 | (2E,4E,6S,7R,8S)-7-[(4-methoxybenzyl)oxy]-2,4,6,8-tetramethyl-2,4-octadecadien-1-ol | C30H50O3 | 详情 | 详情 | |
| (XXIV) | 47178 | (2E,4E,6S,7R,8S)-7-[(4-methoxybenzyl)oxy]-2,4,6,8-tetramethyl-2,4-octadecadienal | C30H48O3 | 详情 | 详情 | |
| (XXV) | 47179 | S-propyl (2S,3S,4E,6E,8S,9R,10S)-3-hydroxy-9-[(4-methoxybenzyl)oxy]-2,4,6,8,10-pentamethyl-4,6-icosadienethioate | C36H60O4S | 详情 | 详情 | |
| (XXVI) | 47180 | S-propyl (2S,3S,4E,6E,8S,9R,10S)-9-[(4-methoxybenzyl)oxy]-2,4,6,8,10-pentamethyl-3-[(triethylsilyl)oxy]-4,6-icosadienethioate | C42H74O4SSi | 详情 | 详情 | |
| (XXVII) | 47181 | (2S,3S,4E,6E,8S,9R,10S)-9-[(4-methoxybenzyl)oxy]-2,4,6,8,10-pentamethyl-3-[(triethylsilyl)oxy]-4,6-icosadienal | C39H68O4Si | 详情 | 详情 |