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【结 构 式】 
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【分子编号】32377 【品名】3-[((7R,8R)-7-[[(triisopropylsilyl)oxy]methyl]-8-[[2-(trimethylsilyl)ethoxy]methoxy]-7,8-dihydronaphtho[2,3-d][1,3]dioxol-6-yl)carbonyl]-1,3-oxazolidin-2-one 【CA登记号】 |
【 分 子 式 】C31H49NO8Si2 【 分 子 量 】619.903 【元素组成】C 60.06% H 7.97% N 2.26% O 20.65% Si 9.06% |
合成路线1
该中间体在本合成路线中的序号：(XIX)The oxidation of the aldehyde group of (XVI) with NaClO2 in tert-butanol affords the corresponding carboxylic acid (XVII), which is condensed with 2-oxazolidinone (XVIII) by means of carbonyldiimidazole (CDI) in THF to give the acyl imidazolide (XIX). The arylation of (XIX) with 3,4,5-trimethoxyphenylmagnesium bromide (XX) in THF yields the expected addition product (XXI), which is cyclized by means of TBAF in hot THF to afford the tetracyclic intermediate (XXII). Isomerization of the cis-lactone ring of (XXII) with LDA in THF affords intermediate (XXIII) with its lactone ring with the correct trans-conformation. Finally, this compound is deprotected with ethyl mercaptane and MgBr2 in ethyl ether to provide the target compound.
| 【1】 Berkowitz, D.B.; et al.; Enzyme-assisted asymmetric total synthesis of (-)-podophyllotoxin and (-)-picropodophyllin. J Org Chem 2000, 65, 3, 847. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XVI) | 32375 | (7R,8R)-7-[[(triisopropylsilyl)oxy]methyl]-8-[[2-(trimethylsilyl)ethoxy]methoxy]-7,8-dihydronaphtho[2,3-d][1,3]dioxole-6-carbaldehyde | C28H46O6Si2 | 详情 | 详情 | |
| (XVII) | 32376 | (7R,8R)-7-[[(triisopropylsilyl)oxy]methyl]-8-[[2-(trimethylsilyl)ethoxy]methoxy]-7,8-dihydronaphtho[2,3-d][1,3]dioxole-6-carboxylic acid | C28H46O7Si2 | 详情 | 详情 | |
| (XVIII) | 21456 | 1,3-oxazolidin-2-one | 497-25-6 | C3H5NO2 | 详情 | 详情 |
| (XIX) | 32377 | 3-[((7R,8R)-7-[[(triisopropylsilyl)oxy]methyl]-8-[[2-(trimethylsilyl)ethoxy]methoxy]-7,8-dihydronaphtho[2,3-d][1,3]dioxol-6-yl)carbonyl]-1,3-oxazolidin-2-one | C31H49NO8Si2 | 详情 | 详情 | |
| (XX) | 32378 | bromo(3,4,5-trimethoxyphenyl)magnesium | C9H11BrMgO3 | 详情 | 详情 | |
| (XXI) | 32379 | 3-[((5R,6S,7R,8R)-7-[[(triisopropylsilyl)oxy]methyl]-5-(3,4,5-trimethoxyphenyl)-8-[[2-(trimethylsilyl)ethoxy]methoxy]-5,6,7,8-tetrahydronaphtho[2,3-d][1,3]dioxol-6-yl)carbonyl]-1,3-oxazolidin-2-one | C40H61NO11Si2 | 详情 | 详情 | |
| (XXII) | 32380 | (5R,5aS,8aR,9R)-5-(3,4,5-trimethoxyphenyl)-9-[[2-(trimethylsilyl)ethoxy]methoxy]-5,8,8a,9-tetrahydrofuro[3',4':6,7]naphtho[2,3-d][1,3]dioxol-6(5aH)-one | C28H36O9Si | 详情 | 详情 | |
| (XXIII) | 32381 | (5R,5aR,8aR,9R)-5-(3,4,5-trimethoxyphenyl)-9-[[2-(trimethylsilyl)ethoxy]methoxy]-5,8,8a,9-tetrahydrofuro[3',4':6,7]naphtho[2,3-d][1,3]dioxol-6(5aH)-one | C28H36O9Si | 详情 | 详情 |