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【结 构 式】 
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【分子编号】30291 【品名】(1S,5S,7R,9R,12R)-10-([[tert-butyl(diphenyl)silyl]oxy]methyl)-7-(4-methoxyphenyl)-3-(phenylselanyl)-6,8-dioxatetracyclo[10.4.1.0(1,5).0(5,9)]heptadec-10-ene-4,17-dione 【CA登记号】 |
【 分 子 式 】C45H48O6SeSi 【 分 子 量 】791.91802 【元素组成】C 68.25% H 6.11% O 12.12% Se 9.97% Si 3.55% |
合成路线1
该中间体在本合成路线中的序号：(XVII)Ketone (XVI) was treated with phenylselanyl chloride and LHMDS yielding the selenium derivative (XVII). Enone (XVIII) was then produced by oxidative elimination of the selenide (XVII). Reduction of the unsaturated ketone (XVIII) with NaBH4 in the presence of CeCl3 gave the 3-beta-allylic alcohol (XIX). This was acylated with myristoyl chloride (XX) to afford ester (XXI). Finally, acid deprotection of the silyl ether and the p-methoxyphenyl acetal of (XXI) furnished the title compound.
| 【1】 Winkler, J.D.; Lewin, N.E.; Blumberg, P.M.; Harrison, S.; Kim, S.; Synthesis and biological evaluation of highly functionalized analogues of ingenol. J Am Chem Soc 1999, 121, 2, 296. |
| 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) | 30290 | (1S,5S,7R,9R,12R)-10-([[tert-butyl(diphenyl)silyl]oxy]methyl)-7-(4-methoxyphenyl)-6,8-dioxatetracyclo[10.4.1.0(1,5).0(5,9)]heptadec-10-ene-4,17-dione | C39H44O6Si | 详情 | 详情 | |
| (XVII) | 30291 | (1S,5S,7R,9R,12R)-10-([[tert-butyl(diphenyl)silyl]oxy]methyl)-7-(4-methoxyphenyl)-3-(phenylselanyl)-6,8-dioxatetracyclo[10.4.1.0(1,5).0(5,9)]heptadec-10-ene-4,17-dione | C45H48O6SeSi | 详情 | 详情 | |
| (XVIII) | 30292 | (1S,5S,7R,9R,12R)-10-([[tert-butyl(diphenyl)silyl]oxy]methyl)-7-(4-methoxyphenyl)-6,8-dioxatetracyclo[10.4.1.0(1,5).0(5,9)]heptadeca-2,10-diene-4,17-dione | C39H42O6Si | 详情 | 详情 | |
| (XIX) | 30293 | (1S,4S,5R,7R,9R,12R)-10-([[tert-butyl(diphenyl)silyl]oxy]methyl)-4-hydroxy-7-(4-methoxyphenyl)-6,8-dioxatetracyclo[10.4.1.0(1,5).0(5,9)]heptadeca-2,10-dien-17-one | C39H44O6Si | 详情 | 详情 | |
| (XX) | 30295 | tetradecanoyl chloride | 112-64-1 | C14H27ClO | 详情 | 详情 |
| (XXI) | 30294 | (1S,4S,5S,7R,9R,12R)-10-([[tert-butyl(diphenyl)silyl]oxy]methyl)-7-(4-methoxyphenyl)-17-oxo-6,8-dioxatetracyclo[10.4.1.0(1,5).0(5,9)]heptadeca-2,10-dien-4-yl myristate | C53H70O7Si | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XVII)Ketone (XVI) was treated with phenylselanyl chloride and LHMDS yielding the selenium derivative (XVII). Enone (XVIII) was then produced by oxidative elimination of the selenide (XVII). Reduction of the unsaturated ketone (XVIII) with NaBH4 in the presence of CeCl3 gave the 3-beta-allylic alcohol (XIX). This was acylated with nonanoyl chloride (XX) to afford ester (XXI). Finally, acid deprotection of the silyl ether and the p-methoxyphenyl acetal of (XXI) furnished the title compound.
| 【1】 Winkler, J.D.; Lewin, N.E.; Blumberg, P.M.; Harrison, S.; Kim, S.; Synthesis and biological evaluation of highly functionalized analogues of ingenol. J Am Chem Soc 1999, 121, 2, 296. |
| 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) | 30290 | (1S,5S,7R,9R,12R)-10-([[tert-butyl(diphenyl)silyl]oxy]methyl)-7-(4-methoxyphenyl)-6,8-dioxatetracyclo[10.4.1.0(1,5).0(5,9)]heptadec-10-ene-4,17-dione | C39H44O6Si | 详情 | 详情 | |
| (XVII) | 30291 | (1S,5S,7R,9R,12R)-10-([[tert-butyl(diphenyl)silyl]oxy]methyl)-7-(4-methoxyphenyl)-3-(phenylselanyl)-6,8-dioxatetracyclo[10.4.1.0(1,5).0(5,9)]heptadec-10-ene-4,17-dione | C45H48O6SeSi | 详情 | 详情 | |
| (XVIII) | 30292 | (1S,5S,7R,9R,12R)-10-([[tert-butyl(diphenyl)silyl]oxy]methyl)-7-(4-methoxyphenyl)-6,8-dioxatetracyclo[10.4.1.0(1,5).0(5,9)]heptadeca-2,10-diene-4,17-dione | C39H42O6Si | 详情 | 详情 | |
| (XIX) | 30293 | (1S,4S,5R,7R,9R,12R)-10-([[tert-butyl(diphenyl)silyl]oxy]methyl)-4-hydroxy-7-(4-methoxyphenyl)-6,8-dioxatetracyclo[10.4.1.0(1,5).0(5,9)]heptadeca-2,10-dien-17-one | C39H44O6Si | 详情 | 详情 | |
| (XX) | 30296 | nonanoyl chloride | 764-85-2 | C9H17ClO | 详情 | 详情 |
| (XXI) | 30297 | (1S,4S,5S,7R,9R,12R)-10-([[tert-butyl(diphenyl)silyl]oxy]methyl)-7-(4-methoxyphenyl)-17-oxo-6,8-dioxatetracyclo[10.4.1.0(1,5).0(5,9)]heptadeca-2,10-dien-4-yl nonanoate | C48H60O7Si | 详情 | 详情 |