(4R,5S)-5-hydroxy-5-(hydroxymethyl)-4-methyl-6-oxo-6-(2-trimethylsilylethoxy)hexanoic acid | 122445-42-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (4R,5S)-5-hydroxy-5-(hydroxymethyl)-4-methyl-6-oxo-6-(2-trimethylsilylethoxy)hexanoic acid
• CAS: 122445-42-5
• 化学式: C₁₃H₂₆O₆Si
• 分子量: 306.431
• InChiKey: DEPNFRJTGMYZDG-ZWNOBZJWSA-N

物化性质

• 沸点：
  452.5±38.0 °C(predicted)
• 密度：
  1.124±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.09
• 重原子数：
  20.0
• 可旋转键数：
  9.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  104.06
• 氢给体数：
  3.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (4R,5S)-5-hydroxy-5-(hydroxymethyl)-4-methyl-6-oxo-6-(2-trimethylsilylethoxy)hexanoic acid 在 盐酸 、 4-二甲氨基吡啶 、 ruthenium trichloride 、 正丁基锂 、 N-环己基异丙基胺 、 camphor-10-sulfonic acid 、 2-氯-1-甲基吡啶碘化物 、 双氧水 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 、 乙腈 为溶剂， 反应 79.17h， 生成 光萼野百合碱
  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：

  (2S,3R)-3,7-Dimethyl-2-hydroxy-2-(hydroxymethyl)-6-octenyl Pivalate 在 ruthenium trichloride 、 titanium(IV) tetraethanolate 、 sodium periodate 、 lithium aluminium tetrahydride 、 重铬酸吡啶 、 二甲基硫 、 camphor-10-sulfonic acid 、 臭氧 、 溶剂黄146 作用下， 以 四氯化碳 、 乙醚 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 112.08h， 生成 (4R,5S)-5-hydroxy-5-(hydroxymethyl)-4-methyl-6-oxo-6-(2-trimethylsilylethoxy)hexanoic acid
  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

文献信息

• Synthesis of the macrolactone alkaloid (+)-usaramine via necic acid coupling to a pyrrolizidine borane
  作者：James D. White、John C. Amedio、Samuel Gut、Lalith Jayasinghe

  DOI：10.1021/jo00279a005

  日期：1989.9
• WHITE, JAMES D.;AMEDIO, JOHN C. (JR);GUT, SAMUEL;JAYASINGHE, LALITH, J. ORG. CHEM., 54,(1989) N8, C. 4268-4270
  作者：WHITE, JAMES D.、AMEDIO, JOHN C. (JR)、GUT, SAMUEL、JAYASINGHE, LALITH

  DOI：——

  日期：——