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【结 构 式】 
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【分子编号】11547 【品名】(4S)-3-[(2S,3S,5S,6S,7S,8E)-2-Allyl-3-hydroxy-9-[(1R,3R,4R)-3-methoxy-4-[(triisopropylsilyl)oxy]cyclohexyl]-6,8-dimethyl-7-[(triethylsilyl)oxy]-5-[(triisopropylsilyl)oxy]-8-nonenoyl]-4-isopropyl-1,3-oxazolidin-2-one 【CA登记号】 |
【 分 子 式 】C51H99NO8Si3 【 分 子 量 】938.6055 【元素组成】C 65.26% H 10.63% N 1.49% O 13.64% Si 8.98% |
合成路线1
该中间体在本合成路线中的序号：(XLVIII)(XLIII) is silylated with TIPS-SO3CF3 to the protected ester (XLIV). The reduction of (XLIV) with diisobutylaluminum hydride yields the primary alcohol (XLV), which is oxidized with the complex pyridine - SO3 to the aldehyde (XLVI). The condensation of (XLVI) with the boron enolate of the oxazolidone (XLVII) affords the oxazolidone derivative (XLVIII), which is treated with methylchloroaluminum N-methoxy-N-methylamide as before to give the methoxyamide (XLIX). Silylation of (XLIX) with TBS-SO3CF3 as usual yields the protected amide (L), which is finally reduced with diisobutylaluminum hydride to the second building group, the aldehyde (LI).
| 【1】 Jones, T.K.; Askin, D.; Mills, S.G.; Reamer, R.A.; Desmond, R.; Volante, R.P.; Tschaen, D.M.; Shinkai, I. (Merck & Co., Inc.); Process for synthesis of FK-506 and tricarbonyl intermediates. EP 0378318; JP 1990233643 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 63306 | C3H9AlClNO | 详情 | 详情 | |||
| (IL) | 11548 | (2S,3S,5S,6S,7S,8E)-2-Allyl-3-hydroxy-N-methoxy-9-[(1R,3R,4R)-3-methoxy-4-[(triisopropylsilyl)oxy]cyclohexyl]-N,6,8-trimethyl-7-[(triethylsilyl)oxy]-5-[(triisopropylsilyl)oxy]-8-nonenamide | C47H95NO7Si3 | 详情 | 详情 | |
| (XLIII) | 11542 | methyl (3S,4R,5S,6E)-3-hydroxy-7-[(1R,3R,4R)-3-methoxy-4-[(triisopropylsilyl)oxy]cyclohexyl]-4,6-dimethyl-5-[(triethylsilyl)oxy]-6-heptenoate | C32H64O6Si2 | 详情 | 详情 | |
| (XLIV) | 11543 | methyl (3S,4S,5S,6E)-7-[(1R,3R,4R)-3-methoxy-4-[(triisopropylsilyl)oxy]cyclohexyl]-4,6-dimethyl-5-[(triethylsilyl)oxy]-3-[(triisopropylsilyl)oxy]-6-heptenoate | C41H84O6Si3 | 详情 | 详情 | |
| (XLV) | 11544 | (3S,4S,5S,6E)-7-[(1R,3R,4R)-3-Methoxy-4-[(triisopropylsilyl)oxy]cyclohexyl]-4,6-dimethyl-5-[(triethylsilyl)oxy]-3-[(triisopropylsilyl)oxy]-6-hepten-1-ol | C40H84O5Si3 | 详情 | 详情 | |
| (XLVI) | 11545 | (3S,4S,5S,6E)-7-[(1R,3R,4R)-3-Methoxy-4-[(triisopropylsilyl)oxy]cyclohexyl]-4,6-dimethyl-5-[(triethylsilyl)oxy]-3-[(triisopropylsilyl)oxy]-6-heptenal | C40H82O5Si3 | 详情 | 详情 | |
| (XLVII) | 11546 | (4S)-4-Isopropyl-3-(4-pentenoyl)-1,3-oxazolidin-2-one | C11H17NO3 | 详情 | 详情 | |
| (XLVIII) | 11547 | (4S)-3-[(2S,3S,5S,6S,7S,8E)-2-Allyl-3-hydroxy-9-[(1R,3R,4R)-3-methoxy-4-[(triisopropylsilyl)oxy]cyclohexyl]-6,8-dimethyl-7-[(triethylsilyl)oxy]-5-[(triisopropylsilyl)oxy]-8-nonenoyl]-4-isopropyl-1,3-oxazolidin-2-one | C51H99NO8Si3 | 详情 | 详情 | |
| (L) | 11549 | (2S,3S,5S,6S,7S,8E)-2-Allyl-3-[[tert-butyl(dimethyl)silyl]oxy]-N-methoxy-9-[(1R,3R,4R)-3-methoxy-4-[(triisopropylsilyl)oxy]cyclohexyl]-N,6,8-trimethyl-7-[(triethylsilyl)oxy]-5-[(triisopropylsilyl)oxy]-8-nonenamide | C53H109NO7Si4 | 详情 | 详情 | |
| (LI) | 11550 | (2S,3S,5S,6S,7S,8E)-2-Allyl-3-[[tert-butyl(dimethyl)silyl]oxy]-9-[(1R,3R,4R)-3-methoxy-4-[(triisopropylsilyl)oxy]cyclohexyl]-6,8-dimethyl-7-[(triethylsilyl)oxy]-5-[(triisopropylsilyl)oxy]-8-nonenal | C51H104O6Si4 | 详情 | 详情 |