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【结 构 式】 
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【分子编号】61301 【品名】(2R)-3-[(2S,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl 4-methylbenzenesulfonate 【CA登记号】 |
【 分 子 式 】C24H40O5SSi 【 分 子 量 】468.7301 【元素组成】C 61.5% H 8.6% O 17.07% S 6.84% Si 5.99% |
合成路线1
该中间体在本合成路线中的序号：(XVI)The synthesis of the dihydropyran intermediate (XX) has been performed as follows: The reduction of the known aldehyde (XIV) with NaBH4 in methanol, followed by reaction with Tbdms-Cl and imidazole in DMF gives the silyl ether (XV), which is selectively deprotected with DDQ in dichloromethane and treated with TsCl and TEA to yield the tosylate (XVI). The reaction of (XVI) with NaCN in hot DMSO, followed by reaction with MeLi in ethyl ether affords the methyl ketone (XVII), which is treated with KHMDS and Ph-NTf2 in THF to provide the enol triflate (XVIII). Finally, this compound is treated with Tms-CH2-MgCl , Pd(PPh3)4 and LiCl in ethyl ether to furnish the target dihydropyran intermediate (XX).
| 【1】 Mulzer, J.; Hanbauer, M.; Total synthesis of the antitumor agent (-)-laulimalide. Tetrahedron Lett 2002, 43, 18, 3381. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XIV) | 61207 | 2-((2R,6S)-6-{(2R)-3-[(4-methoxybenzyl)oxy]-2-methylpropyl}-5,6-dihydro-2H-pyran-2-yl)acetaldehyde | C19H26O4 | 详情 | 详情 | |
| (XV) | 61208 | tert-butyl(dimethyl)silyl 2-((2R,6S)-6-{(2R)-3-[(4-methoxybenzyl)oxy]-2-methylpropyl}-5,6-dihydro-2H-pyran-2-yl)ethyl ether; tert-butyl[2-((2R,6S)-6-{(2R)-3-[(4-methoxybenzyl)oxy]-2-methylpropyl}-5,6-dihydro-2H-pyran-2-yl)ethoxy]dimethylsilane | C25H42O4Si | 详情 | 详情 | |
| (XVI) | 61301 | (2R)-3-[(2S,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl 4-methylbenzenesulfonate | C24H40O5SSi | 详情 | 详情 | |
| (XVII) | 61302 | (4R)-5-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-4-methyl-2-pentanone | C19H36O3Si | 详情 | 详情 | |
| (XVIII) | 61303 | 1-{(2R)-3-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}vinyl trifluoromethanesulfonate | C20H35F3O5SSi | 详情 | 详情 | |
| (XIX) | 61304 | Trimethylsilylmethylmagnesium Chloride; (Trimethylsilyl)methylmagnesium chloride Solution; Chloro[(trimethylsilyl)methyl]magnesium; (TRIMETHYLSILYLMETHYL)MAGNESIUM CHLORIDE; (TRIMETHYLSILYL)METHYLMAGNESIUM CHL. SOL | 13170-43-9 | C4H11ClMgSi | 详情 | 详情 |
| (XX) | 61305 | tert-butyl(dimethyl)[2-((2R,6R)-6-{(2S)-2-methyl-4-[(trimethylsilyl)methyl]-4-pentenyl}-5,6-dihydro-2H-pyran-2-yl)ethoxy]silane; tert-butyl(dimethyl)silyl 2-((2R,6R)-6-{(2S)-2-methyl-4-[(trimethylsilyl)methyl]-4-pentenyl}-5,6-dihydro-2H-pyran-2-yl)ethyl ether | C23H46O2Si2 | 详情 | 详情 |