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【结 构 式】 
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【分子编号】30286 【品名】(1S,6R,9R,11S,13R,16S)-8-([[tert-butyl(diphenyl)silyl]oxy]methyl)-16-hydroxy-11-(4-methoxyphenyl)-10,12-dioxatetracyclo[7.6.1.1(1,6).0(13,16)]heptadec-7-en-17-one 【CA登记号】 |
【 分 子 式 】C39H46O6Si 【 分 子 量 】638.87614 【元素组成】C 73.32% H 7.26% O 15.03% Si 4.4% |
合成路线1
该中间体在本合成路线中的序号：(XII)Elimination of the sulfate group of (XI) with DBU in refluxing toluene led, after acidic workup, to the formation of the allylic alcohol (XII). Oxidative cleavage of the p-methoxyphenyl acetal of (XII) with DDQ produced regioselectively the p-methoxybenzoate ester (XIII). Further treatment of (XIII) with p--anisaldehyde dimethyl acetal (VII) gave the acetal (XIV). Ester hydrolysis of (XIV), followed by oxidation of the resulting alcohol (XV) with Dess-Martin periodinane afforded ketone (XVI).
| 【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 |
|---|---|---|---|---|---|---|
| (XI) | 30285 | (1S,4R,6R,8S,9S,13S,15R)-13-([[tert-butyl(diphenyl)silyl]oxy]methyl)-6-(4-methoxyphenyl)-5,7,10,12-tetraoxa-11lambda(6)-thiapentacyclo[13.4.1.0(1,9).0(4,9).0(8,13)]icosane-11,11,20-trione | C39H46O9SSi | 详情 | 详情 | |
| (XII) | 30286 | (1S,6R,9R,11S,13R,16S)-8-([[tert-butyl(diphenyl)silyl]oxy]methyl)-16-hydroxy-11-(4-methoxyphenyl)-10,12-dioxatetracyclo[7.6.1.1(1,6).0(13,16)]heptadec-7-en-17-one | C39H46O6Si | 详情 | 详情 | |
| (XIII) | 30287 | (1S,4R,5S,6R,9R)-7-([[tert-butyl(diphenyl)silyl]oxy]methyl)-5,6-dihydroxy-14-oxotricyclo[7.4.1.0(1,5)]tetradec-7-en-4-yl 4-methoxybenzoate | C39H46O7Si | 详情 | 详情 | |
| (XIV) | 30288 | (1S,4R,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)]heptadec-10-en-4-yl 4-methoxybenzoate | C47H52O8Si | 详情 | 详情 | |
| (XV) | 30289 | (1S,4R,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)]heptadec-10-en-17-one | C39H46O6Si | 详情 | 详情 | |
| (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 |
合成路线2
该中间体在本合成路线中的序号：(XII)Elimination of the sulfate of (XI) with DBU in refluxing toluene led, after acidic workup, to the formation of the allylic alcohol (XII). Oxidative cleavage of the p-methoxyphenyl acetal of (XII) with DDQ produced regioselectively the p-methoxybenzoate ester (XIII). Further treatment of (XIII) with p-anisaldehyde dimethyl acetal (VII) gave the acetal (XIV). Ester hydrolysis of (XIV), followed by oxidation of the resulting alcohol (XV) with Dess-Martin periodinane afforded ketone (XVI).
| 【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 |
|---|---|---|---|---|---|---|
| (XI) | 30285 | (1S,4R,6R,8S,9S,13S,15R)-13-([[tert-butyl(diphenyl)silyl]oxy]methyl)-6-(4-methoxyphenyl)-5,7,10,12-tetraoxa-11lambda(6)-thiapentacyclo[13.4.1.0(1,9).0(4,9).0(8,13)]icosane-11,11,20-trione | C39H46O9SSi | 详情 | 详情 | |
| (XII) | 30286 | (1S,6R,9R,11S,13R,16S)-8-([[tert-butyl(diphenyl)silyl]oxy]methyl)-16-hydroxy-11-(4-methoxyphenyl)-10,12-dioxatetracyclo[7.6.1.1(1,6).0(13,16)]heptadec-7-en-17-one | C39H46O6Si | 详情 | 详情 | |
| (XIII) | 30287 | (1S,4R,5S,6R,9R)-7-([[tert-butyl(diphenyl)silyl]oxy]methyl)-5,6-dihydroxy-14-oxotricyclo[7.4.1.0(1,5)]tetradec-7-en-4-yl 4-methoxybenzoate | C39H46O7Si | 详情 | 详情 | |
| (XIV) | 30288 | (1S,4R,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)]heptadec-10-en-4-yl 4-methoxybenzoate | C47H52O8Si | 详情 | 详情 | |
| (XV) | 30289 | (1S,4R,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)]heptadec-10-en-17-one | C39H46O6Si | 详情 | 详情 | |
| (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 |