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【结 构 式】 
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【分子编号】61724 【品名】2-(trimethylsilyl)ethyl (E)-3-((3S,5R,6S)-5,14-bis{[tert-butyl(dimethyl)silyl]oxy}-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-1-propenyl[(2Z,4Z)-2,4-heptadienoyl]carbamate 【CA登记号】 |
【 分 子 式 】C44H73NO7Si3 【 分 子 量 】812.32266 【元素组成】C 65.06% H 9.06% N 1.72% O 13.79% Si 10.37% |
合成路线1
该中间体在本合成路线中的序号：(XXVII)The demethylation of (XXI) by means of BBr3 gives the hydroxyaldehyde (XXII), which is oxidized to the corresponding carboxylic acid (XXIII) by means of NaClO2. The protection of the phenolic OH group of (XXIII) by means of Tbdms-OTf and TEA yields the silyl ether (XXIV), which is submitted to a Curtius rearrangement by means of isobutyl chloroformate, NaN3 and 2-(trimethylsilyl)ethanol, affording the carbamate (XXV). The acylation of carbamate (XXV) with heptadienoyl chloride (XXVI) and NaHMDS provides the advanced intermediate (XXVII), which is finally deprotected by successive treatments with TBAF and with HF/pyridine to provide the target Salicylhalamide A.
| 【1】 Smith, A.B.; Zheng, J.Y.; Total synthesis of (-)-salicylihalamide A and related congeners. Tetrahedron 2002, 58, 33, 6455. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XIV) | 56950 | (E)-4-((3S,5R,6S)-5,14-bis{[tert-butyl(dimethyl)silyl]oxy}-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-2-butenoic acid | C32H52O6Si2 | 详情 | 详情 | |
| (XXI) | 61720 | (E)-4-((3S,5R,6S)-5-{[tert-butyl(dimethyl)silyl]oxy}-14-methoxy-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-2-butenal | C27H40O5Si | 详情 | 详情 | |
| (XXII) | 61721 | (E)-4-((3S,5R,6S)-5-{[tert-butyl(dimethyl)silyl]oxy}-14-hydroxy-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-2-butenal | C26H38O5Si | 详情 | 详情 | |
| (XXIII) | 61722 | (E)-4-((3S,5R,6S)-5-{[tert-butyl(dimethyl)silyl]oxy}-14-hydroxy-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-2-butenoic acid | C26H38O6Si | 详情 | 详情 | |
| (XXV) | 61723 | 2-(trimethylsilyl)ethyl (E)-3-((3S,5R,6S)-5,14-bis{[tert-butyl(dimethyl)silyl]oxy}-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-1-propenylcarbamate | C37H65NO6Si3 | 详情 | 详情 | |
| (XXVI) | 61725 | (2Z,4Z)-2,4-heptadienoyl chloride | C7H9ClO | 详情 | 详情 | |
| (XXVII) | 61724 | 2-(trimethylsilyl)ethyl (E)-3-((3S,5R,6S)-5,14-bis{[tert-butyl(dimethyl)silyl]oxy}-6-methyl-1-oxo-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-3-yl)-1-propenyl[(2Z,4Z)-2,4-heptadienoyl]carbamate | C44H73NO7Si3 | 详情 | 详情 |