【结 构 式】 |
【分子编号】60196 【品名】9-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-3-hydroxy-N,2,6-trimethyl-N-(methyloxy)-6-nonenamide 【CA登记号】 |
【 分 子 式 】C19H39NO4Si 【 分 子 量 】373.6085 【元素组成】C 61.08% H 10.52% N 3.75% O 17.13% Si 7.52% |
合成路线1
该中间体在本合成路线中的序号:(IV)Preparation of fragment (VIII) is illustrated in Scheme 24509401a. Aldol condensation of aldehyde (I) with (R)-4-benzyl-3-propionyl-2-oxazolidinone (II) mediated by dibutylboron triflate gives the syn aldol adduct (III). This is converted to the Weinreb amide (IV) by treatment with N,O-dimethyl hydroxylamine in the presence of trimethylaluminium. After silylation of the secondary hydroxyl group of (IV), the resultant bis-silyl ether (V) is selectively desilylated at the primary hydroxyl group with p-toluenesulfonic acid and tetrabutylammonium bisulfate, to afford alcohol (VI). Dess-Martin oxidation of (VI) gives the aldehyde (VII), which is then subjected to Corey-Fuchs olefination with CBr4 and PPh3 to produce the gem-dibromo olefin (VIII)
【1】 Evans, D.A.; Starr, J.T.; A cascade cycloaddition strategy leading to the total synthesis of (-)-FR182877. Angew Chem. Int Ed 2002, 41, 10, 1787. |
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) | 60194 | 7-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-4-methyl-4-heptenal | C14H28O2Si | 详情 | 详情 | |
(II) | 25713 | (4S)-4-benzyl-3-propionyl-1,3-oxazolidin-2-one | C13H15NO3 | 详情 | 详情 | |
(III) | 60195 | (4R)-4-benzyl-3-((2R,3S,6E)-9-{[tert-butyl(dimethyl)silyl]oxy}-3-hydroxy-2,6-dimethyl-6-nonenoyl)-1,3-oxazolidin-2-one | C27H43NO5Si | 详情 | 详情 | |
(IV) | 60196 | 9-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-3-hydroxy-N,2,6-trimethyl-N-(methyloxy)-6-nonenamide | C19H39NO4Si | 详情 | 详情 | |
(V) | 60197 | 3,9-bis{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-N,2,6-trimethyl-N-(methyloxy)-6-nonenamide | C25H53NO4Si2 | 详情 | 详情 | |
(VI) | 60198 | 3-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-9-hydroxy-N,2,6-trimethyl-N-(methyloxy)-6-nonenamide | C19H39NO4Si | 详情 | 详情 | |
(VII) | 60199 | 3-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-N,2,6-trimethyl-N-(methyloxy)-9-oxo-6-nonenamide | C19H37NO4Si | 详情 | 详情 | |
(VIII) | 60352 | 10,10-dibromo-3-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-N,2,6-trimethyl-N-(methyloxy)-6,9-decadienamide | C20H37Br2NO3Si | 详情 | 详情 |