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【结 构 式】 
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【分子编号】46067 【品名】(1R)-1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]-1,2-ethanediol 【CA登记号】 |
【 分 子 式 】C10H19BrO3 【 分 子 量 】267.16306 【元素组成】C 44.96% H 7.17% Br 29.91% O 17.97% |
合成路线1
该中间体在本合成路线中的序号：(XI)The regio- and stereoselective hydrolysis of (2R,3R)-epoxygeraniol (V) with HClO4 in THF/water gives the trihydroxy compound (VI), which is selectively benzoylated with benzoyl chloride, TEA and DMAP to yield the dibenzoate (VII). The reaction of (VII) with TBCO in nitromethane affords a mixture of tetrahydrofuran (VIII) and tetrahydropyran (IX), which are separated by chromatography. The desired isomer (X) is hydrolyzed with K2CO3 in methanol to provide the alpha-diol (XI), which is finally oxidized with NaIO4 in THF/water to furnish the target aldehydic intermediate (IV).
| 【1】 Forsyth, G.J.; Gonzalez, I.C.; Total synthesis of tryrsiferyl 23-acetate, a specific inhibitor of protein phosphatase 2A and anti-leukemic inducer of apoptosis. J Am Chem Soc 2000, 122, 38, 9099. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (IV) | 46060 | (2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-carbaldehyde | C9H15BrO2 | 详情 | 详情 | |
| (V) | 46061 | [(2R,3R)-3-methyl-3-(4-methyl-3-pentenyl)oxiranyl]methanol | C10H18O2 | 详情 | 详情 | |
| (VI) | 46062 | (2R,3S)-3,7-dimethyl-6-octene-1,2,3-triol | C10H20O3 | 详情 | 详情 | |
| (VII) | 46063 | (2R,3S)-2,3-bis(benzoyloxy)-3,7-dimethyl-6-octenyl benzoate | C31H32O6 | 详情 | 详情 | |
| (VIII) | 46064 | (2R)-2-(benzoyloxy)-2-[(2S)-5-(1-bromo-1-methylethyl)-2-methyltetrahydro-2-furanyl]ethyl benzoate | C24H27BrO5 | 详情 | 详情 | |
| (IX) | 46065 | (1R)-2-(benzoyloxy)-1-[(2S)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]ethyl benzoate | C24H27BrO5 | 详情 | 详情 | |
| (X) | 46066 | (1R)-2-(benzoyloxy)-1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]ethyl benzoate | C24H27BrO5 | 详情 | 详情 | |
| (XI) | 46067 | (1R)-1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]-1,2-ethanediol | C10H19BrO3 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XI)The regio- and stereoselective hydrolysis of (2R,3R)-epoxygeraniol (V) with HClO4 in THF/water gives the trihydroxy compound (VI), which is selectively benzoylated with benzoyl chloride, TEA and DMAP to yield the dibenzoate (VII). The reaction of (VII) with TBCO in nitromethane affords a mixture of tetrahydrofuran (VIII) and tetrahydropyran (IX), which are separated by chromatography. The desired isomer (X) is hydrolyzed with K2CO3 in methanol to provide the alpha-diol (XI), which is finally oxidized with NaIO4 in THF/water to furnish the target aldehydic intermediate (IV).
| 【1】 Forsyth, G.J.; Gonzalez, I.C.; Total synthesis of tryrsiferyl 23-acetate, a specific inhibitor of protein phosphatase 2A and anti-leukemic inducer of apoptosis. J Am Chem Soc 2000, 122, 38, 9099. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (IV) | 46060 | (2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-carbaldehyde | C9H15BrO2 | 详情 | 详情 | |
| (V) | 46061 | [(2R,3R)-3-methyl-3-(4-methyl-3-pentenyl)oxiranyl]methanol | C10H18O2 | 详情 | 详情 | |
| (VI) | 46062 | (2R,3S)-3,7-dimethyl-6-octene-1,2,3-triol | C10H20O3 | 详情 | 详情 | |
| (VII) | 46063 | (2R,3S)-2,3-bis(benzoyloxy)-3,7-dimethyl-6-octenyl benzoate | C31H32O6 | 详情 | 详情 | |
| (VIII) | 46064 | (2R)-2-(benzoyloxy)-2-[(2S)-5-(1-bromo-1-methylethyl)-2-methyltetrahydro-2-furanyl]ethyl benzoate | C24H27BrO5 | 详情 | 详情 | |
| (IX) | 46065 | (1R)-2-(benzoyloxy)-1-[(2S)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]ethyl benzoate | C24H27BrO5 | 详情 | 详情 | |
| (X) | 46066 | (1R)-2-(benzoyloxy)-1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]ethyl benzoate | C24H27BrO5 | 详情 | 详情 | |
| (XI) | 46067 | (1R)-1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]-1,2-ethanediol | C10H19BrO3 | 详情 | 详情 |
合成路线3
该中间体在本合成路线中的序号：(XI)The regio- and stereoselective hydrolysis of (2R,3R)-epoxygeraniol (V) with HClO4 in THF/water gives the trihydroxy compound (VI), which is selectively benzoylated with benzoyl chloride, TEA and DMAP to yield the dibenzoate (VII). The reaction of (VII) with TBCO in nitromethane affords a mixture of tetrahydrofuran (VIII) and tetrahydropyran (IX), which are separated by chromatography. The desired isomer (X) is hydrolyzed with K2CO3 in methanol to provide the alpha-diol (XI), which is finally oxidized with NaIO4 in THF/water to furnish the target aldehydic intermediate (IV).
| 【1】 Forsyth, G.J.; Gonzalez, I.C.; Total synthesis of tryrsiferyl 23-acetate, a specific inhibitor of protein phosphatase 2A and anti-leukemic inducer of apoptosis. J Am Chem Soc 2000, 122, 38, 9099. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (IV) | 46060 | (2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-carbaldehyde | C9H15BrO2 | 详情 | 详情 | |
| (V) | 46061 | [(2R,3R)-3-methyl-3-(4-methyl-3-pentenyl)oxiranyl]methanol | C10H18O2 | 详情 | 详情 | |
| (VI) | 46062 | (2R,3S)-3,7-dimethyl-6-octene-1,2,3-triol | C10H20O3 | 详情 | 详情 | |
| (VII) | 46063 | (2R,3S)-2,3-bis(benzoyloxy)-3,7-dimethyl-6-octenyl benzoate | C31H32O6 | 详情 | 详情 | |
| (VIII) | 46064 | (2R)-2-(benzoyloxy)-2-[(2S)-5-(1-bromo-1-methylethyl)-2-methyltetrahydro-2-furanyl]ethyl benzoate | C24H27BrO5 | 详情 | 详情 | |
| (IX) | 46065 | (1R)-2-(benzoyloxy)-1-[(2S)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]ethyl benzoate | C24H27BrO5 | 详情 | 详情 | |
| (X) | 46066 | (1R)-2-(benzoyloxy)-1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]ethyl benzoate | C24H27BrO5 | 详情 | 详情 | |
| (XI) | 46067 | (1R)-1-[(2S,5R)-5-bromo-2,6,6-trimethyltetrahydro-2H-pyran-2-yl]-1,2-ethanediol | C10H19BrO3 | 详情 | 详情 |