【结 构 式】 |
【分子编号】49354 【品名】[4-[(1E,3S)-3-hydroxy-2-methyl-1,5-hexadienyl]-1,3-thiazol-2-yl]methyl 2,2,2-trichloroethyl carbonate 【CA登记号】 |
【 分 子 式 】C14H16Cl3NO4S 【 分 子 量 】400.70948 【元素组成】C 41.96% H 4.02% Cl 26.54% N 3.5% O 15.97% S 8% |
合成路线1
该中间体在本合成路线中的序号:(VI)The intermediate iodovinyl compound (XI) has been obtained as follows: The reaction of 2-(hydroxymethyl)thiazole-4-carboxylic acid ethyl ester (I) with Troc-Cl and pyridine in dichloromethane gives the protected compound (II), which is reduced with DIBAL in the same solvent to yield the carbaldehyde (III). The condensation of aldehyde (III) with phosphorane (IV) in refluxing benzene affords the unsaturated aldehyde (V), which is asymmetrically allylated by means of (+)-diisopinocampheyl(allyl)borane in pentane to provide the chiral secondary alcohol (VI). The reaction of (VI) with Tbdms-Cl and lutidine in dichloromethane gives the silyl ether (VII), which is oxidized at the terminal double bond by means of OsO4 and Pb(OAc)4 to yield the aldehyde (VIII). The condensation of (VIII) with phosphorane (IX) and LiOH in THF affords the iodovinyl compound (X), which is finally treated with Troc-Cl and pyridine to provide the desired iodovinyl intermediate (XI).
【1】 Zhang, X.-G.; Chappell, M.D.; Lee, C.B.; Kuduk, S.D.; Danishefsky, S.J.; Chou, T.-C.; Wang, Z.-G.; Stachel, S.J.; Total synthesis and antitumor activity of 12,13-dexoxyepothilone F: An unexpected solvolysis problem at C15, mediated by remote substitution at C21. J Org Chem 2000, 65, 20, 6525. |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
(I) | 49350 | ethyl 2-(hydroxymethyl)-1,3-thiazole-4-carboxylate | C7H9NO3S | 详情 | 详情 | |
(II) | 49351 | ethyl 2-([[(2,2,2-trichloroethoxy)carbonyl]oxy]methyl)-1,3-thiazole-4-carboxylate | C10H10Cl3NO5S | 详情 | 详情 | |
(III) | 49352 | (4-formyl-1,3-thiazol-2-yl)methyl 2,2,2-trichloroethyl carbonate | C8H6Cl3NO4S | 详情 | 详情 | |
(IV) | 39940 | 2-(triphenylphosphoranylidene)propanal | C21H19OP | 详情 | 详情 | |
(V) | 49353 | [4-[(E)-2-methyl-3-oxo-1-propenyl]-1,3-thiazol-2-yl]methyl 2,2,2-trichloroethyl carbonate | C11H10Cl3NO4S | 详情 | 详情 | |
(VI) | 49354 | [4-[(1E,3S)-3-hydroxy-2-methyl-1,5-hexadienyl]-1,3-thiazol-2-yl]methyl 2,2,2-trichloroethyl carbonate | C14H16Cl3NO4S | 详情 | 详情 | |
(VII) | 49355 | [4-((1E,3S)-3-[[tert-butyl(dimethyl)silyl]oxy]-2-methyl-1,5-hexadienyl)-1,3-thiazol-2-yl]methyl 2,2,2-trichloroethyl carbonate | C20H30Cl3NO4SSi | 详情 | 详情 | |
(VIII) | 49356 | [4-((E,3S)-3-[[tert-butyl(dimethyl)silyl]oxy]-2-methyl-5-oxo-1-pentenyl)-1,3-thiazol-2-yl]methyl 2,2,2-trichloroethyl carbonate | C19H28Cl3NO5SSi | 详情 | 详情 | |
(IX) | 42754 | (1-iodoethylidene)(triphenyl)phosphorane | C20H18IP | 详情 | 详情 | |
(X) | 49357 | [4-((1E,3S,5Z)-3-[[tert-butyl(dimethyl)silyl]oxy]-6-iodo-2-methyl-1,5-heptadienyl)-1,3-thiazol-2-yl]methanol | C18H30INO2SSi | 详情 | 详情 | |
(XI) | 49358 | [4-((1E,3S,5Z)-3-[[tert-butyl(dimethyl)silyl]oxy]-6-iodo-2-methyl-1,5-heptadienyl)-1,3-thiazol-2-yl]methyl 2,2,2-trichloroethyl carbonate | C21H31Cl3INO4SSi | 详情 | 详情 |