2-trimethylsilylethyl (4S)-4-[(2R)-5-[[(1R,8R)-7-(hydroxymethyl)-2,3,5,8-tetrahydro-1H-pyrrolizin-1-yl]oxy]-5-oxopentan-2-yl]-2,2-dimethyl-1,3-dioxolane-4-carboxylate | 139608-83-6

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: 2-trimethylsilylethyl (4S)-4-[(2R)-5-[[(1R,8R)-7-(hydroxymethyl)-2,3,5,8-tetrahydro-1H-pyrrolizin-1-yl]oxy]-5-oxopentan-2-yl]-2,2-dimethyl-1,3-dioxolane-4-carboxylate
• CAS: 139608-83-6
• 化学式: C₂₄H₄₁NO₇Si
• 分子量: 483.678
• InChiKey: CAAHOTPBXJQEMI-PRAZENRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.72
• 重原子数：
  33.0
• 可旋转键数：
  10.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  94.53
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  2-trimethylsilylethyl (4S)-4-[(2R)-5-[[(1R,8R)-7-(hydroxymethyl)-2,3,5,8-tetrahydro-1H-pyrrolizin-1-yl]oxy]-5-oxopentan-2-yl]-2,2-dimethyl-1,3-dioxolane-4-carboxylate 在 四丁基氟化铵 、 甲基磺酰氯 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 3.0h， 生成 (1'R,4S,6'R,17'R)-2,2,6'-trimethylspiro[1,3-dioxolane-4,7'-2,9-dioxa-14-azatricyclo[9.5.1.014,17]heptadec-11-ene]-3',8'-dione
  参考文献：
  名称：

  Stereoselective synthesis of the pyrrolizidine alkaloids (-)-integerrimine and (+)-usaramine

  摘要：

  Two routes to the pyrrolizidine alkaloid (-)-integerrimine (1) are described. The first, starting from methyl (R)-(-)-3-hydroxy-2-methylpropionate, proceeded in 19 steps to integerrinecic acid lactone (5) which was transformed to the necic acid derivative 30. The latter was coupled to protected retronecine 31, and the synthesis of 1 was completed by lactonization employing Vedejs' protocol. A second, shorter synthesis of (-)-1 was accomplished via 5, starting from (R)-(+)-beta-citronellol (36). This pathway invoked Katsuki-Sharpless epoxidation of 42 for stereoselective construction of the tertiary alcohol of integerrinecic acid. A parallel sequence proceeding via the stereoisomeric epoxide 44 led to the necic acid segment 75 of the alkaloid (+)-usaramine (2). This acid was coupled to the retronecine borane 82 and then lactonized to 2.

  DOI：

  10.1021/jo00034a017
• 作为产物：
  描述：

  [(S)-2-((R)-1,5-Dimethyl-hex-4-enyl)-oxiranyl]-methanol 在 titanium(IV) isopropylate 、 4-二甲氨基吡啶 、 ruthenium trichloride 、 titanium(IV) tetraethanolate 、 sodium periodate 、 lithium aluminium tetrahydride 、 重铬酸吡啶 、 正丁基锂 、 二甲基硫 、 camphor-10-sulfonic acid 、 氢氟酸 、 臭氧 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 四氯化碳 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 、 苯 为溶剂， 反应 119.58h， 生成 2-trimethylsilylethyl (4S)-4-[(2R)-5-[[(1R,8R)-7-(hydroxymethyl)-2,3,5,8-tetrahydro-1H-pyrrolizin-1-yl]oxy]-5-oxopentan-2-yl]-2,2-dimethyl-1,3-dioxolane-4-carboxylate
  参考文献：
  名称：

  Stereoselective synthesis of the pyrrolizidine alkaloids (-)-integerrimine and (+)-usaramine

  摘要：

  Two routes to the pyrrolizidine alkaloid (-)-integerrimine (1) are described. The first, starting from methyl (R)-(-)-3-hydroxy-2-methylpropionate, proceeded in 19 steps to integerrinecic acid lactone (5) which was transformed to the necic acid derivative 30. The latter was coupled to protected retronecine 31, and the synthesis of 1 was completed by lactonization employing Vedejs' protocol. A second, shorter synthesis of (-)-1 was accomplished via 5, starting from (R)-(+)-beta-citronellol (36). This pathway invoked Katsuki-Sharpless epoxidation of 42 for stereoselective construction of the tertiary alcohol of integerrinecic acid. A parallel sequence proceeding via the stereoisomeric epoxide 44 led to the necic acid segment 75 of the alkaloid (+)-usaramine (2). This acid was coupled to the retronecine borane 82 and then lactonized to 2.

  DOI：

  10.1021/jo00034a017