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【结 构 式】 
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【分子编号】63138 【品名】(4S)-2-{(2R)-3-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-5-[(4-methoxybenzyl)oxy]-2-(phenylsulfonyl)-1,4-pentanediol 【CA登记号】 |
【 分 子 式 】C36H56O8SSi 【 分 子 量 】676.98734 【元素组成】C 63.87% H 8.34% O 18.91% S 4.74% Si 4.15% |
合成路线1
该中间体在本合成路线中的序号：(XLIII)The cleavage of the benzyl ether of (XXXVII) by means of Li/NH3, followed by treatment with I2 and PPh3 gives the iodide derivative (XXXVIII), which is condensed with tetrahydrofuranone (XXXIX) (obtained by reaction of epoxide (XL) with methyl 2-(phenylsulfonyl)acetate (XLI) and NaH) by means of NaH to afford the adduct (XLII). The reductive cleavage of the tetrahydrofuranone (XLII) by means of Red-Al provides the diol (XLIII), which is treated with Ph-COCl and Na/Hg to give the methylene derivative (XLIV). The reaction of (XLIV) with Mom-Cl and DIEA yields the Mom-ether compound (XLV), which is selectively deprotected by means of DDQ to afford the primary alcohol (XLVI). The oxidation of (XLVI) with oxalyl chloride provides the carbaldehyde (XLVII).
| 【1】 Ghosh, A.K.; Wang, Y.; Kim, J.T.; Total synthesis of microtubule-stabilizing agent (-)-laulimalide. J Org Chem 2001, 66, 26, 8973. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXXVII) | 63129 | benzyl (2R)-3-[(2S,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl ether; (2-{(2R,6S)-6-[(2R)-3-(benzyloxy)-2-methylpropyl]-5,6-dihydro-2H-pyran-2-yl}ethoxy)(tert-butyl)dimethylsilane | C24H40O3Si | 详情 | 详情 | |
| (XXXVIII) | 63133 | tert-butyl(2-{(2R,6S)-6-[(2R)-3-iodo-2-methylpropyl]-5,6-dihydro-2H-pyran-2-yl}ethoxy)dimethylsilane; tert-butyl(dimethyl)silyl 2-{(2R,6S)-6-[(2R)-3-iodo-2-methylpropyl]-5,6-dihydro-2H-pyran-2-yl}ethyl ether | C17H33IO2Si | 详情 | 详情 | |
| (XXXIX) | 63134 | (5S)-5-{[(4-methoxybenzyl)oxy]methyl}-3-(phenylsulfonyl)dihydro-2(3H)-furanone | C19H20O6S | 详情 | 详情 | |
| (XL) | 63135 | 4-methoxybenzyl (2R)oxiranylmethyl ether; (2R)-2-{[(4-methoxybenzyl)oxy]methyl}oxirane | C11H14O3 | 详情 | 详情 | |
| (XLI) | 63136 | methyl 2-(phenylsulfonyl)acetate | C9H10O4S | 详情 | 详情 | |
| (XLII) | 63137 | (5S)-3-{(2R)-3-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-5-{[(4-methoxybenzyl)oxy]methyl}-3-(phenylsulfonyl)dihydro-2(3H)-furanone | C36H52O8SSi | 详情 | 详情 | |
| (XLIII) | 63138 | (4S)-2-{(2R)-3-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-5-[(4-methoxybenzyl)oxy]-2-(phenylsulfonyl)-1,4-pentanediol | C36H56O8SSi | 详情 | 详情 | |
| (XLIV) | 63139 | (2S)-4-{(2S)-3-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-1-[(4-methoxybenzyl)oxy]-4-penten-2-ol | C30H50O5Si | 详情 | 详情 | |
| (XLV) | 63140 | tert-butyl(dimethyl)silyl 2-((2R,6R)-6-{(2S)-4-[(2S)-3-[(4-methoxybenzyl)oxy]-2-(methoxymethoxy)propyl]-2-methyl-4-pentenyl}-5,6-dihydro-2H-pyran-2-yl)ethyl ether; tert-butyl[2-((2R,6R)-6-{(2S)-4-[(2S)-3-[(4-methoxybenzyl)oxy]-2-(methoxymethoxy)propyl]-2-methyl-4-pentenyl}-5,6-dihydro-2H-pyran-2-yl)ethoxy]dimethylsilane | C32H54O6Si | 详情 | 详情 | |
| (XLVI) | 63141 | (2S)-4-{(2S)-3-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-2-(methoxymethoxy)-4-penten-1-ol | C24H46O5Si | 详情 | 详情 | |
| (XLVII) | 63142 | (2S)-4-{(2S)-3-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-2-(methoxymethoxy)-4-pentenal | C24H44O5Si | 详情 | 详情 |