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【结 构 式】 
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【分子编号】34988 【品名】(5aR,8aS,9R)-9-(3,4,5-trimethoxyphenyl)-5a,6,8a,9-tetrahydrofuro[3',4':6,7]naphtho[2,3-d][1,3]dioxole-5,8-dione 【CA登记号】 |
【 分 子 式 】C22H20O8 【 分 子 量 】412.396 【元素组成】C 64.07% H 4.89% O 31.04% |
合成路线1
该中间体在本合成路线中的序号：(XXXIV)The oxidation of (XXXI) with pyridinium dichromate (PDC) gives the ketoester (XXXII). The reaction of (XXXII) with formaldehyde/NaOH and then with p-toluenesulfonic acid gives the hydroxymethyl lactone (XXXIII), which is submitted to a thermal extrusion of formaldehyde yielding (XXXIV). The regioselective reduction of the ketonic group of (XXXIV) with LiAl(OtBU)3H in THF affords hydroxylactone (XXXV) with undesired steric configuration at the lactone ring. The silylation of (XXXV) with TBDMS-OTf affords the silyl ether (XXXVI), which is isomerized with LiHMDS in THF giving (XXXVII) with the right configuration. Finally, this compound is desilylated to the target compound with triethylammonium fluoride in acetonitrile.
| 【1】 Andrews, R.C.; et al.; Asymetric total synthesis of (-)-podophyllotoxin. J Am Chem Soc 1988, 110, 23, 7854. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXXI) | 34985 | methyl (5R,6S,7S)-7-([[tert-butyl(dimethyl)silyl]oxy]methyl)-8-hydroxy-5-(3,4,5-trimethoxyphenyl)-5,6,7,8-tetrahydronaphtho[2,3-d][1,3]dioxole-6-carboxylate | C29H40O9Si | 详情 | 详情 | |
| (XXXII) | 34986 | methyl (5R,6S,7S)-7-([[tert-butyl(dimethyl)silyl]oxy]methyl)-8-oxo-5-(3,4,5-trimethoxyphenyl)-5,6,7,8-tetrahydronaphtho[2,3-d][1,3]dioxole-6-carboxylate | C29H38O9Si | 详情 | 详情 | |
| (XXXIII) | 34987 | (5aS,8aS,9R)-5a-(hydroxymethyl)-9-(3,4,5-trimethoxyphenyl)-5a,6,8a,9-tetrahydrofuro[3',4':6,7]naphtho[2,3-d][1,3]dioxole-5,8-dione | C23H22O9 | 详情 | 详情 | |
| (XXXIV) | 34988 | (5aR,8aS,9R)-9-(3,4,5-trimethoxyphenyl)-5a,6,8a,9-tetrahydrofuro[3',4':6,7]naphtho[2,3-d][1,3]dioxole-5,8-dione | C22H20O8 | 详情 | 详情 | |
| (XXXV) | 34989 | (5R,5aS,8aR,9R)-9-hydroxy-5-(3,4,5-trimethoxyphenyl)-5,8,8a,9-tetrahydrofuro[3',4':6,7]naphtho[2,3-d][1,3]dioxol-6(5aH)-one | C22H22O8 | 详情 | 详情 | |
| (XXXVI) | 34990 | (5R,5aS,8aR,9R)-9-[[tert-butyl(dimethyl)silyl]oxy]-5-(3,4,5-trimethoxyphenyl)-5,8,8a,9-tetrahydrofuro[3',4':6,7]naphtho[2,3-d][1,3]dioxol-6(5aH)-one | C28H36O8Si | 详情 | 详情 | |
| (XXXVII) | 34991 | (5R,5aR,8aR,9R)-9-[[tert-butyl(dimethyl)silyl]oxy]-5-(3,4,5-trimethoxyphenyl)-5,8,8a,9-tetrahydrofuro[3',4':6,7]naphtho[2,3-d][1,3]dioxol-6(5aH)-one | C28H36O8Si | 详情 | 详情 |