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【结 构 式】 
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【分子编号】46168 【品名】((3S)-4-[[tert-butyl(dimethyl)silyl]oxy]-3-methylbutyl)(triphenyl)phosphonium iodide 【CA登记号】 |
【 分 子 式 】C29H40IOPSi 【 分 子 量 】590.599732 【元素组成】C 58.98% H 6.83% I 21.49% O 2.71% P 5.24% Si 4.76% |
合成路线1
该中间体在本合成路线中的序号：(VII)Synthesis of intermediate triphenylphosphonium salt (VII): The condensation of the chiral oxazolidinone (I) with cinnamyl bromide (II) by means of NaHMDS in THF gives the adduct (III), which is treated with LiBH4 in Et2O/water to yield the alcohol (IV). The protection of (IV) with Tbdms-Cl and imidazole in DMF affords the silyl ether (V), which is treated with ozone and reduced with NaBH4 to provide the alcohol (VI). The reaction of (VI) with I2 and PPh3 gives the desired triphenylphosphonium iodide (VII).
| 【1】 Mulzer, J.; et al.; A novel highly stereoselective total synthesis of epothilone B and of its (12R,13R) acetonide. Tetrahedron Lett 2000, 41, 40, 7635. |
| 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) | 46163 | (4R,5S)-4-methyl-5-phenyl-3-propionyl-1,3-oxazolidin-2-one | C13H15NO3 | 详情 | 详情 | |
| (II) | 21131 | 1-[(E)-3-bromo-1-propenyl]benzene | 4392-24-9 | C9H9Br | 详情 | 详情 |
| (III) | 46164 | (4R,5S)-4-methyl-3-[(2S,4E)-2-methyl-5-phenyl-4-pentenoyl]-5-phenyl-1,3-oxazolidin-2-one | C22H23NO3 | 详情 | 详情 | |
| (IV) | 46165 | (2S,4E)-2-methyl-5-phenyl-4-penten-1-ol | C12H16O | 详情 | 详情 | |
| (V) | 46166 | tert-butyl(dimethyl)silyl (2S,4E)-2-methyl-5-phenyl-4-pentenyl ether; tert-butyl(dimethyl)[[(2S,4E)-2-methyl-5-phenyl-4-pentenyl]oxy]silane | C18H30OSi | 详情 | 详情 | |
| (VI) | 46167 | (3S)-4-[[tert-butyl(dimethyl)silyl]oxy]-3-methyl-1-butanol | C11H26O2Si | 详情 | 详情 | |
| (VII) | 46168 | ((3S)-4-[[tert-butyl(dimethyl)silyl]oxy]-3-methylbutyl)(triphenyl)phosphonium iodide | C29H40IOPSi | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(VII)Assembly of the target compound: The condensation of the phosphonium salt (VII) with the aldehyde (XV) by means of NaHMDS in THF gives the adduct (XIX), which is debenzylated and hydrogenated with H2 over Pd/Al2O3 in ethanol and oxidized with NaIO4 and RuCl3 to yield the carboxylic acid (XX). The activation of (XX) with pivaloyl chloride affords the anhydride (XXI), which is condensed with the lithium oxazolidinone (XXII) to provide the cyclic amide (XXIII). The enantioselective hydroxylation of (XXIII) by means of the Davis oxaziridine and NaHMDS gives the alpha-hydroxyamide (XXIV), which is treated with N,O-dimethylhydroxylamine (XXV) to yield the methoxyamide (XXVI). The protection of the OH group of (XXVI) with Tbdms-OTf and lutidine affords the silyl ether (XXVII), which is treated with MeLi in THF, affording the methyl ketone (XXVIII). The condensation of (XXVIII) with tributyl(2-methylthiazol-4-ylmethyl)phosphonium chloride (XXIX) by means of KHMDS in THF provides the adduct (XXX).
| 【1】 Mulzer, J.; et al.; A novel highly stereoselective total synthesis of epothilone B and of its (12R,13R) acetonide. Tetrahedron Lett 2000, 41, 40, 7635. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (VII) | 46168 | ((3S)-4-[[tert-butyl(dimethyl)silyl]oxy]-3-methylbutyl)(triphenyl)phosphonium iodide | C29H40IOPSi | 详情 | 详情 | |
| (XV) | 46175 | (4S,5R)-5-[3-(benzyloxy)propyl]-2,2,4-trimethyl-1,3-dioxolane-4-carbaldehyde | C17H24O4 | 详情 | 详情 | |
| (XIX) | 46176 | benzyl 3-[(4R,5R)-5-((E,4S)-5-[[tert-butyl(dimethyl)silyl]oxy]-4-methyl-1-pentenyl)-2,2,5-trimethyl-1,3-dioxolan-4-yl]propyl ether; [((2S,4E)-5-[(4R,5R)-5-[3-(benzyloxy)propyl]-2,2,4-trimethyl-1,3-dioxolan-4-yl]-2-methyl-4-pentenyl)oxy](tert-butyl)dimethylsilane | C28H48O4Si | 详情 | 详情 | |
| (XX) | 46177 | 3-[(4R,5R)-5-((4S)-5-[[tert-butyl(dimethyl)silyl]oxy]-4-methylpentyl)-2,2,5-trimethyl-1,3-dioxolan-4-yl]propionic acid | C21H42O5Si | 详情 | 详情 | |
| (XXI) | 46178 | 2-[(4R,5R)-5-((4S)-5-[[tert-butyl(dimethyl)silyl]oxy]-4-methylpentyl)-2,2,5-trimethyl-1,3-dioxolan-4-yl]propionic 1,1-dimethylpropionic anhydride | C26H50O6Si | 详情 | 详情 | |
| (XXII) | 46185 | [(4S,5R)-4-methyl-2-oxo-5-phenyl-1,3-oxazolidin-3-yl]lithium | C10H10LiNO2 | 详情 | 详情 | |
| (XXIII) | 46179 | (4S,5R)-3-[3-[(4R,5R)-5-((4S)-5-[[tert-butyl(dimethyl)silyl]oxy]-4-methylpentyl)-2,2,5-trimethyl-1,3-dioxolan-4-yl]propanoyl]-4-methyl-5-phenyl-1,3-oxazolidin-2-one | C31H51NO6Si | 详情 | 详情 | |
| (XXIV) | 46180 | (4S,5R)-3-[(2S)-3-[(4R,5R)-5-((4S)-5-[[tert-butyl(dimethyl)silyl]oxy]-4-methylpentyl)-2,2,5-trimethyl-1,3-dioxolan-4-yl]-2-hydroxypropanoyl]-4-methyl-5-phenyl-1,3-oxazolidin-2-one | C31H51NO7Si | 详情 | 详情 | |
| (XXV) | 13361 | (Methoxyamino)methane; N,O-Dimethylhydroxylamine | 1117-97-1 | C2H7NO | 详情 | 详情 |
| (XXVI) | 46181 | (2S)-3-[(4R,5R)-5-((4S)-5-[[tert-butyl(dimethyl)silyl]oxy]-4-methylpentyl)-2,2,5-trimethyl-1,3-dioxolan-4-yl]-2-hydroxy-N-methoxy-N-methylpropanamide | C23H47NO6Si | 详情 | 详情 | |
| (XXVII) | 46182 | (2S)-2-[[tert-butyl(dimethyl)silyl]oxy]-3-[(4R,5R)-5-((4S)-5-[[tert-butyl(dimethyl)silyl]oxy]-4-methylpentyl)-2,2,5-trimethyl-1,3-dioxolan-4-yl]-N-methoxy-N-methylpropanamide | C29H61NO6Si2 | 详情 | 详情 | |
| (XXVIII) | 46183 | (3S)-3-[[tert-butyl(dimethyl)silyl]oxy]-4-[(4R,5R)-5-((4S)-5-[[tert-butyl(dimethyl)silyl]oxy]-4-methylpentyl)-2,2,5-trimethyl-1,3-dioxolan-4-yl]-2-butanone | C28H58O5Si2 | 详情 | 详情 | |
| (XXIX) | 40820 | tributyl[(2-methyl-1,3-thiazol-4-yl)methyl]phosphonium chloride | C17H33ClNPS | 详情 | 详情 | |
| (XXX) | 46184 | tert-butyl(dimethyl)silyl (2S)-5-[(4R,5R)-5-[(2S,3E)-2-[[tert-butyl(dimethyl)silyl]oxy]-3-methyl-4-(2-methyl-1,3-thiazol-4-yl)-3-butenyl]-2,2,4-trimethyl-1,3-dioxolan-4-yl]-2-methylpentyl ether; 4-[(E,3S)-3-[[tert-butyl(dimethyl)silyl]oxy]-4-[(4R,5R)-5-((4S)-5-[[tert-butyl(dimethyl)silyl]oxy]-4-methylpentyl)-2,2,5-trimethyl-1,3-dioxolan-4-yl]-2-methyl-1-butenyl]-2-methyl-1,3-thiazole | C33H63NO4SSi2 | 详情 | 详情 |