4-Oxo-pentanoic acid (S)-2-cyclopentyl-1-[(2R,3S)-3-(1-hydroxy-1-methyl-ethyl)-oxiranyl]-allyl ester | 132101-46-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 4-Oxo-pentanoic acid (S)-2-cyclopentyl-1-[(2R,3S)-3-(1-hydroxy-1-methyl-ethyl)-oxiranyl]-allyl ester
• CAS: 132101-46-3
• 化学式: C₁₈H₂₈O₅
• 分子量: 324.417
• InChiKey: ZXTLFADYJCHOFT-BBWFWOEESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.55
• 重原子数：
  23.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  76.13
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  4-Oxo-pentanoic acid (S)-2-cyclopentyl-1-[(2R,3S)-3-(1-hydroxy-1-methyl-ethyl)-oxiranyl]-allyl ester 在 sodium tetrahydroborate 、 水 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以85%的产率得到threo-6-cyclopentyl-2,5-dihydroxy-3,4-epoxy-2-methyl-6-heptene
  参考文献：
  名称：

  Total synthesis of spatol and other spatane diterpenes

  摘要：

  Total syntheses of three spatane diterpenes stoechospermol (1), 5(R),15(R),18-trihydroxyspata-13,16(E)-diene (2), and (+)-spatol (3) were accomplished from a common intermediate, diol 7. The total synthesis established as R the absolute configuration at the 15-position in 2. Novel stereospecific transformations of 2,3-epoxy-1,4-diols into vicinal diepoxides were demonstrated and exploited for assembling the sensitive allylic diepoxide in the side chain of spatol. This new synthetic method allows the conversion of both 1,2-threo-2,3-trans- and 1,2-erythro-2,3-trans-2,3-epoxy-1,4-diols into vicinal 1,2-cis-2,3-erythro-1,3-diepoxides. Unexpected stability toward hydroxide anion was found for the allylic diepoxide functional array. This observation provides presumptive evidence that acid catalysis is operative in the epoxide cleaving substitution reaction of spatol by the weakly nucleophilic chloride anion that gives chlorohydrin 4. A proclivity for erythro-selective epoxidation of allylic silyl ethers was found. The utility of C-silyl substituents for reversing this stereoselectivity, i.e., favoring threo-selective epoxidation of allylic silyl ethers, was established.

  DOI：

  10.1021/ja00008a044
• 作为产物：
  描述：

  2-cyclopentylacrylaldehyde 在 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 bis(acetylacetonate)oxovanadium 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 碳酸氢钠 、 三乙胺 作用下， 以 乙二醇二甲醚 、 乙醇 、 二氯甲烷 为溶剂， 反应 9.33h， 生成 4-Oxo-pentanoic acid (S)-2-cyclopentyl-1-[(2R,3S)-3-(1-hydroxy-1-methyl-ethyl)-oxiranyl]-allyl ester
  参考文献：
  名称：

  Total synthesis of spatol and other spatane diterpenes

  摘要：

  Total syntheses of three spatane diterpenes stoechospermol (1), 5(R),15(R),18-trihydroxyspata-13,16(E)-diene (2), and (+)-spatol (3) were accomplished from a common intermediate, diol 7. The total synthesis established as R the absolute configuration at the 15-position in 2. Novel stereospecific transformations of 2,3-epoxy-1,4-diols into vicinal diepoxides were demonstrated and exploited for assembling the sensitive allylic diepoxide in the side chain of spatol. This new synthetic method allows the conversion of both 1,2-threo-2,3-trans- and 1,2-erythro-2,3-trans-2,3-epoxy-1,4-diols into vicinal 1,2-cis-2,3-erythro-1,3-diepoxides. Unexpected stability toward hydroxide anion was found for the allylic diepoxide functional array. This observation provides presumptive evidence that acid catalysis is operative in the epoxide cleaving substitution reaction of spatol by the weakly nucleophilic chloride anion that gives chlorohydrin 4. A proclivity for erythro-selective epoxidation of allylic silyl ethers was found. The utility of C-silyl substituents for reversing this stereoselectivity, i.e., favoring threo-selective epoxidation of allylic silyl ethers, was established.

  DOI：

  10.1021/ja00008a044