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【结 构 式】 
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【分子编号】62116 【品名】(2S,3R,6R)-3,6-dimethyl-2-[4-(trimethylsilyl)-3-butynyl]-3,6-dihydro-2H-pyran-4-yl triethylsilyl ether; (4-{(2S,3R,6R)-3,6-dimethyl-4-[(triethylsilyl)oxy]-3,6-dihydro-2H-pyran-2-yl}-1-butynyl)(trimethyl)silane 【CA登记号】 |
【 分 子 式 】C20H38O2Si2 【 分 子 量 】366.69152 【元素组成】C 65.51% H 10.45% O 8.73% Si 15.32% |
合成路线1
该中间体在本合成路线中的序号：(VIII)Hetero Diels-Alder reaction between diene (VI) and aldehyde (VII) in the presence of chiral chromium complex furnishes the optically active dihydropyran compound (VIII). Subsequent oxidation of the silyl enol ether moiety of (VIII) with m CPBA under Rubottom conditions affords the alpha-hydroxy ketone (IX). Reduction of ketone (IX) is accomplished via the tosyl hydrazone (X), which is then reduced to (XI) employing NaBH3CN. Desilylation of (XI) with tetrabutylammonium fluoride gives the terminal acetylene (XII), which is further isomerized to the thermodynamically more stable internal alkyne (XIII) in the presence of potassium tert-butoxide in DMSO. Treatment of (XIII) with Schwartz's reagent, followed by quenching of the vinylzirconium intermediate with I2 leads to the vinyl iodide (XIV). After conversion of alcohol (XIV) into the chloromethanesulfonate (XV), displacement with LiN3 provides azide (XVI).
| 【1】 Thompson, C.F.; Jamison, T.F; Jacobsen, E.N.; Total synthesis of FR901464. Convergent assembly of chiral componenents prepared by asymmetric catalysis. J Am Chem Soc 2000, 122, 45, 10482. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (VI) | 62114 | triethyl({(E)-1-[(Z)ethylidene]-2-butenyl}oxy)silane; (E)-1-[(Z)ethylidene]-2-butenyl triethylsilyl ether | C12H24OSi | 详情 | 详情 | |
| (VII) | 62115 | 5-(trimethylsilyl)-4-pentynal | C8H14OSi | 详情 | 详情 | |
| (VIII) | 62116 | (2S,3R,6R)-3,6-dimethyl-2-[4-(trimethylsilyl)-3-butynyl]-3,6-dihydro-2H-pyran-4-yl triethylsilyl ether; (4-{(2S,3R,6R)-3,6-dimethyl-4-[(triethylsilyl)oxy]-3,6-dihydro-2H-pyran-2-yl}-1-butynyl)(trimethyl)silane | C20H38O2Si2 | 详情 | 详情 | |
| (IX) | 62117 | (2R,3R,5R,6S)-3-hydroxy-2,5-dimethyl-6-[4-(trimethylsilyl)-3-butynyl]tetrahydro-4H-pyran-4-one | C14H24O3Si | 详情 | 详情 | |
| (X) | 62118 | N'-{(2R,3S,5S,6S)-3-hydroxy-2,5-dimethyl-6-[4-(trimethylsilyl)-3-butynyl]tetrahydro-4H-pyran-4-ylidene}-4-methylbenzenesulfonohydrazide | C21H32N2O4SSi | 详情 | 详情 | |
| (XI) | 62119 | (2R,3S,5S,6S)-2,5-dimethyl-6-[4-(trimethylsilyl)-3-butynyl]tetrahydro-2H-pyran-3-ol | C14H26O2Si | 详情 | 详情 | |
| (XII) | 62120 | (2R,3S,5S,6S)-6-(3-butynyl)-2,5-dimethyltetrahydro-2H-pyran-3-ol | C11H18O2 | 详情 | 详情 | |
| (XIII) | 62121 | (2R,3S,5S,6S)-6-(2-butynyl)-2,5-dimethyltetrahydro-2H-pyran-3-ol | C11H18O2 | 详情 | 详情 | |
| (XIV) | 62122 | (2R,3S,5S,6S)-6-[(E)-3-iodo-2-butenyl]-2,5-dimethyltetrahydro-2H-pyran-3-ol | C11H19IO2 | 详情 | 详情 | |
| (XV) | 62123 | (2R,3S,5S,6S)-6-[(E)-3-iodo-2-butenyl]-2,5-dimethyltetrahydro-2H-pyran-3-yl chloromethanesulfonate | C12H20ClIO4S | 详情 | 详情 | |
| (XVI) | 62124 | (2R,3R,5S,6S)-6-[(E)-3-iodo-2-butenyl]-2,5-dimethyltetrahydro-2H-pyran-3-yl azide; (2R,3R,5S,6S)-3-azido-6-[(E)-3-iodo-2-butenyl]-2,5-dimethyltetrahydro-2H-pyran | C11H18IN3O | 详情 | 详情 |