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【结 构 式】 
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【分子编号】40275 【品名】(3R,4S,6S,9aS)-6-[(E,3S)-3-hydroxy-1-decenyl]-4-methyloctahydro-2H-quinolizin-3-yl acetate 【CA登记号】 |
【 分 子 式 】C22H39NO3 【 分 子 量 】365.5566 【元素组成】C 72.28% H 10.75% N 3.83% O 13.13% |
合成路线1
该中间体在本合成路线中的序号：(XLIII)During the reduction of mesylate (XLI) with LiAlH4, one of the triisopropylsilyl groups was selectively removed to afford alcohol (XLII). In contrast, when the same process was applied to the anti-isomer of (XXXVIII), the desired quinolizidine (XLI) was obtained along with a high amount of rearranged product. Acetylation of alcohol (XLII) and subsequent desilylation with aqueous HF gave the allylic alcohol (XLIII). Dehydration to the desired diene (XLV) was achieved by way of the allyl sulfide (XLIV), prepared by treatment of alcohol (XLIII) with N-phenylthiophthalimide and tributylphosphine. Subsequent oxidation of (XLIV) with oxone and thermal syn elimination of the intermediate sulfoxide furnished the title diene.
| 【1】 Ha, J.D.; Cha, J.K.; Total synthesis of clavepictines A and B. Diastereoselective cyclization of delta-aminoallenes. J Am Chem Soc 1999, 121, 43, 10012. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XLI) | 40273 | (1R,4S,6S,7R,9aR)-6-methyl-7-[(triisopropylsilyl)oxy]-4-[(E,3S)-3-[(triisopropylsilyl)oxy]-1-decenyl]octahydro-2H-quinolizin-1-yl methanesulfonate | C39H79NO5SSi2 | 详情 | 详情 | |
| (XLII) | 40274 | (3R,4S,6S,9aS)-4-methyl-6-[(E,3S)-3-[(triisopropylsilyl)oxy]-1-decenyl]octahydro-2H-quinolizin-3-ol | C29H57NO2Si | 详情 | 详情 | |
| (XLIII) | 40275 | (3R,4S,6S,9aS)-6-[(E,3S)-3-hydroxy-1-decenyl]-4-methyloctahydro-2H-quinolizin-3-yl acetate | C22H39NO3 | 详情 | 详情 | |
| (XLIV) | 40276 | (3R,4S,6S,9aS)-4-methyl-6-[(E)-3-(phenylsulfanyl)-1-decenyl]octahydro-2H-quinolizin-3-yl acetate | C28H43NO2S | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XLIII)During the reduction of mesylate (XLI) with LiAlH4, one of the triisopropylsilyl groups was selectively removed to afford alcohol (XLII). In contrast, when the same process was applied to the anti-isomer of (XXXVIII), the desired quinolizidine (XLI) was obtained along with a high amount of rearranged product. Acetylation of alcohol (XLII) and subsequent desilylation with aqueous HF gave the allylic alcohol (XLIII). Dehydration to the desired diene (XLV) was achieved by way of the allyl sulfide (XLIV), prepared by treatment of alcohol (XLIII) with N-phenylthiophthalimide and tributylphosphine. Subsequent oxidation of (XLIV) with oxone and thermal syn elimination of the intermediate sulfoxide gave diene (XLV). Finally, the title compound was obtained by basic hydrolysis of the acetate ester of (XLV) with K2CO3 in MeOH.
| 【1】 Ha, J.D.; Cha, J.K.; Total synthesis of clavepictines A and B. Diastereoselective cyclization of delta-aminoallenes. J Am Chem Soc 1999, 121, 43, 10012. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XLI) | 40273 | (1R,4S,6S,7R,9aR)-6-methyl-7-[(triisopropylsilyl)oxy]-4-[(E,3S)-3-[(triisopropylsilyl)oxy]-1-decenyl]octahydro-2H-quinolizin-1-yl methanesulfonate | C39H79NO5SSi2 | 详情 | 详情 | |
| (XLII) | 40274 | (3R,4S,6S,9aS)-4-methyl-6-[(E,3S)-3-[(triisopropylsilyl)oxy]-1-decenyl]octahydro-2H-quinolizin-3-ol | C29H57NO2Si | 详情 | 详情 | |
| (XLIII) | 40275 | (3R,4S,6S,9aS)-6-[(E,3S)-3-hydroxy-1-decenyl]-4-methyloctahydro-2H-quinolizin-3-yl acetate | C22H39NO3 | 详情 | 详情 | |
| (XLIV) | 40276 | (3R,4S,6S,9aS)-4-methyl-6-[(E)-3-(phenylsulfanyl)-1-decenyl]octahydro-2H-quinolizin-3-yl acetate | C28H43NO2S | 详情 | 详情 | |
| (XLV) | 40277 | (3R,4S,6S,9aS)-6-[(1E,3E)-1,3-decadienyl]-4-methyloctahydro-2H-quinolizin-3-yl acetate | C22H37NO2 | 详情 | 详情 |