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【结 构 式】 
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【分子编号】57155 【品名】(1R,3S)-3-{[tert-butyl(dimethyl)silyl]oxy}-5-oxocyclohexyl acetate 【CA登记号】 |
【 分 子 式 】C14H26O4Si 【 分 子 量 】286.44354 【元素组成】C 58.7% H 9.15% O 22.34% Si 9.8% |
合成路线1
该中间体在本合成路线中的序号：(VI)The reaction of cis,cis-cyclohexane-1,3,5-triol (I) with Ac2O and pyridine gives the triacetate (II), which is monodeacylated by means of porcine liver esterase at pH 7 to yield the diacetate (III). The silylation of the OH group of (III) with Tbdms-Cl , TEA and DMAP in dichloromethane affords the silyl ether (IV), which is submitted to desymmetrization by enzymatic hydrolysis with porcine liver esterase to provide the chiral cyclohexanol derivative (V). The oxidation of (V) by means of PCC in dichloromethane gives the chiral cyclohexanone (VI), which is finally treated with DBU in dichloromethane to yield the intermediate 5(S)-(Tbdms-O)-2-cyclohexenone (VII).
| 【1】 Kalkote, U.R.; et al.; Simple, efficient chemoenzymatic synthesis of (S)-5-(tert-butyldimethylsilyloxy)-2-cyclohexenone and enantiomeric ketone intermediates of 19-Nor-1alpha,25-dihydroxyvitamin D3. J Org Chem 2001, 66, 24, 8277. |
| 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) | 11800 | 1,3,5-Cyclohexanetriol; cis,cis-1,3,5-Cyclohexanetriol dihydrate | 50409-12-6 | C6H12O3 | 详情 | 详情 |
| (II) | 49040 | 3,5-bis(acetoxy)cyclohexyl acetate | C12H18O6 | 详情 | 详情 | |
| (III) | 57152 | (1R,3S)-3-(acetyloxy)-5-hydroxycyclohexyl acetate | C10H16O5 | 详情 | 详情 | |
| (IV) | 57153 | (1R,3S)-3-(acetyloxy)-5-{[tert-butyl(dimethyl)silyl]oxy}cyclohexyl acetate | C16H30O5Si | 详情 | 详情 | |
| (V) | 57154 | (1S,3R,5R)-3-{[tert-butyl(dimethyl)silyl]oxy}-5-hydroxycyclohexyl acetate | C14H28O4Si | 详情 | 详情 | |
| (VI) | 57155 | (1R,3S)-3-{[tert-butyl(dimethyl)silyl]oxy}-5-oxocyclohexyl acetate | C14H26O4Si | 详情 | 详情 | |
| (VII) | 57138 | (5S)-5-{[tert-butyl(dimethyl)silyl]oxy}-2-cyclohexen-1-one | C12H22O2Si | 详情 | 详情 |