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【结 构 式】 
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【分子编号】26249 【品名】(3S,6R,7S,8S,12Z,15S,16E)-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxo-7-[[(2,2,2-trichloroethoxy)carbonyl]oxy]-3,15-bis[(triethylsilyl)oxy]-12,16-heptadecadienoic acid 【CA登记号】 |
【 分 子 式 】C42H72Cl3NO8SSi2 【 分 子 量 】913.63072 【元素组成】C 55.22% H 7.94% Cl 11.64% N 1.53% O 14.01% S 3.51% Si 6.15% |
合成路线1
该中间体在本合成路线中的序号：(XI)Further treatment of (X) with Et3SiOTf and 2,6-lutidine protected both 3- and 15-hydroxyl groups as the triethylsilyl ethers and cleaved the tert-butyl ester to yield carboxylic acid (XI). The bis(triethylsilyl)-protected diol (XI) was selectively hydrolyzed to the required 15-hydroxy acid (XII) upon treatment with cold 0.12 M HCl in MeOH. Macrolactonization of (XII) was then performed by means of 2,4,6-trichlorobenzoyl chloride, Et3N and DMAP yielding (XIII). Removal of the trichloroethoxycarbonyl protecting group from the resulting lactone (XIII) employing SmI2 and a catalytic amount of NiI2 in THF at -78 C yielded (XIV). Finally, desilylation of (XIV) with HF-pyridine afforded the target compound.
| 【1】 Harris, C.R.; et al.; New chemical synthesis of the promising cancer chemotherapeutic agent 12,13-desoxyepothilone B: Discovery of a surprising long-range effect on the diastereoselectivity of an aldol condensation. J Am Chem Soc 1999, 121, 30, 7050. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (X) | 26248 | tert-butyl (3S,6R,7S,8S,12Z,15S,16E)-3,15-dihydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxo-7-[[(2,2,2-trichloroethoxy)carbonyl]oxy]-12,16-heptadecadienoate | C34H52Cl3NO8S | 详情 | 详情 | |
| (XI) | 26249 | (3S,6R,7S,8S,12Z,15S,16E)-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxo-7-[[(2,2,2-trichloroethoxy)carbonyl]oxy]-3,15-bis[(triethylsilyl)oxy]-12,16-heptadecadienoic acid | C42H72Cl3NO8SSi2 | 详情 | 详情 | |
| (XII) | 26250 | (3S,6R,7S,8S,12Z,15S,16E)-15-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxo-7-[[(2,2,2-trichloroethoxy)carbonyl]oxy]-3-[(triethylsilyl)oxy]-12,16-heptadecadienoic acid | C36H58Cl3NO8SSi | 详情 | 详情 | |
| (XIII) | 26251 | (4S,7R,8S,9S,16S)-5,5,7,9,13-pentamethyl-16-[(E)-1-methyl-2-(2-methyl-1,3-thiazol-4-yl)ethenyl]-2,6-dioxo-4-[(triethylsilyl)oxy]oxa-13-cyclohexadecen-8-yl 2,2,2-trichloroethyl carbonate | C36H56Cl3NO7SSi | 详情 | 详情 | |
| (XIV) | 26252 | (4S,7R,8S,9S,16S)-8-hydroxy-5,5,7,9,13-pentamethyl-16-[(E)-1-methyl-2-(2-methyl-1,3-thiazol-4-yl)ethenyl]-4-[(triethylsilyl)oxy]oxa-13-cyclohexadecene-2,6-dione | C33H55NO5SSi | 详情 | 详情 |