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【结 构 式】 
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【分子编号】42475 【品名】1-allyl 4-[(2S,3R,6S,8R,9S)-2-[(1E,3E)-5-(allyloxy)-3-methyl-5-oxo-1,3-pentadienyl]-3-butyl-9-methyl-8-[(E)-3-methyl-4-oxo-2-butenyl]-1,7-dioxaspiro[5.5]undec-3-yl] succinate 【CA登记号】 |
【 分 子 式 】C35H50O9 【 分 子 量 】614.7766 【元素组成】C 68.38% H 8.2% O 23.42% |
合成路线1
该中间体在本合成路线中的序号：(XXIX)The oxidation of (XXV) with DMP in dichloromethane gives the aldehyde (XXVII), which is condensed with phosphorane (XXVIII) in refluxing toluene to yield aldehyde (XXIX). The reduction of (XXIX) with Zn(BH4)2 in ethyl ether affords alcohol (XXX), which is condensed with 2-sulfanylbenzothiazole (XXXI) by means of Bu3P and TMAD in benzene providing the thioether (XXXII). The oxidation of (XXXII) with Mo7O24(NH4)6 and H2O2 in ethanol gives the sulfone (XXXIII), which is condensed with the aldehyde (XXXIV) by means of LHMDS in THF to yield intermediate (XXXV). The selective monodesilylation of (XXXV) with PPTS in chloroform/methanol, followed by oxidation with DMP, affords the aldehyde (XXXVI).
| 【1】 Shimizu, T.; et al.; Total synthesis of reveromycin A. Org Lett 2000, 2, 14, 2153. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXV) | 42472 | 1-allyl 4-[(2S,3R,6S,8R,9S)-2-[(1E,3E)-5-(allyloxy)-3-methyl-5-oxo-1,3-pentadienyl]-3-butyl-8-(2-hydroxyethyl)-9-methyl-1,7-dioxaspiro[5.5]undec-3-yl] succinate | C32H48O9 | 详情 | 详情 | |
| (XXVII) | 42474 | 1-allyl 4-[(2S,3R,6S,8R,9S)-2-[(1E,3E)-5-(allyloxy)-3-methyl-5-oxo-1,3-pentadienyl]-3-butyl-9-methyl-8-(2-oxoethyl)-1,7-dioxaspiro[5.5]undec-3-yl] succinate | C32H46O9 | 详情 | 详情 | |
| (XXVIII) | 39940 | 2-(triphenylphosphoranylidene)propanal | C21H19OP | 详情 | 详情 | |
| (XXIX) | 42475 | 1-allyl 4-[(2S,3R,6S,8R,9S)-2-[(1E,3E)-5-(allyloxy)-3-methyl-5-oxo-1,3-pentadienyl]-3-butyl-9-methyl-8-[(E)-3-methyl-4-oxo-2-butenyl]-1,7-dioxaspiro[5.5]undec-3-yl] succinate | C35H50O9 | 详情 | 详情 | |
| (XXX) | 42476 | 1-allyl 4-[(2S,3R,6S,8R,9S)-2-[(1E,3E)-5-(allyloxy)-3-methyl-5-oxo-1,3-pentadienyl]-3-butyl-8-[(E)-4-hydroxy-3-methyl-2-butenyl]-9-methyl-1,7-dioxaspiro[5.5]undec-3-yl] succinate | C35H52O9 | 详情 | 详情 | |
| (XXXI) | 24677 | 1,3-benzothiazol-2-ylhydrosulfide | 149-30-4 | C7H5NS2 | 详情 | 详情 |
| (XXXII) | 42477 | 1-allyl 4-[(2S,3R,6S,8R,9S)-2-[(1E,3E)-5-(allyloxy)-3-methyl-5-oxo-1,3-pentadienyl]-8-[(E)-4-(1,3-benzothiazol-2-ylsulfanyl)-3-methyl-2-butenyl]-3-butyl-9-methyl-1,7-dioxaspiro[5.5]undec-3-yl] succinate | C42H55NO8S2 | 详情 | 详情 | |
| (XXXIII) | 42478 | 1-allyl 4-[(2S,3R,6S,8R,9S)-2-[(1E,3E)-5-(allyloxy)-3-methyl-5-oxo-1,3-pentadienyl]-8-[(E)-4-(1,3-benzothiazol-2-ylsulfonyl)-3-methyl-2-butenyl]-3-butyl-9-methyl-1,7-dioxaspiro[5.5]undec-3-yl] succinate | C42H55NO10S2 | 详情 | 详情 | |
| (XXXIV) | 42479 | (2R,3S)-2-[[tert-butyl(dimethyl)silyl]oxy]-3-methyl-4-[(triethylsilyl)oxy]butanal | C17H38O3Si2 | 详情 | 详情 | |
| (XXXV) | 42480 | 1-allyl 4-((2S,3R,6S,8R,9S)-2-[(1E,3E)-5-(allyloxy)-3-methyl-5-oxo-1,3-pentadienyl]-3-butyl-8-[(2E,4E,6S,7S)-6-[[tert-butyl(dimethyl)silyl]oxy]-3,7-dimethyl-8-[(triethylsilyl)oxy]-2,4-octadienyl]-9-methyl-1,7-dioxaspiro[5.5]undec-3-yl) succinate | C52H88O10Si2 | 详情 | 详情 | |
| (XXXVI) | 42481 | 1-allyl 4-[(2S,3R,6S,8R,9S)-2-[(1E,3E)-5-(allyloxy)-3-methyl-5-oxo-1,3-pentadienyl]-3-butyl-8-((2E,4E,6S,7R)-6-[[tert-butyl(dimethyl)silyl]oxy]-3,7-dimethyl-8-oxo-2,4-octadienyl)-9-methyl-1,7-dioxaspiro[5.5]undec-3-yl] succinate | C46H72O10Si | 详情 | 详情 |