tert-butyl-dimethyl-[(2S)-1-[(1R,2S,6S)-3-methyl-6-prop-1-en-2-yl-2-trimethylsilyloxycyclohex-3-en-1-yl]but-3-yn-2-yl]oxysilane | 1454915-79-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: tert-butyl-dimethyl-[(2S)-1-[(1R,2S,6S)-3-methyl-6-prop-1-en-2-yl-2-trimethylsilyloxycyclohex-3-en-1-yl]but-3-yn-2-yl]oxysilane
• CAS: 1454915-79-7
• 化学式: C₂₃H₄₂O₂Si₂
• 分子量: 406.756
• InChiKey: JBNXAIMIHYUHRX-GXRSIYKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.78
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tert-butyl-dimethyl-[(2S)-1-[(1R,2S,6S)-3-methyl-6-prop-1-en-2-yl-2-trimethylsilyloxycyclohex-3-en-1-yl]but-3-yn-2-yl]oxysilane 在 dicobalt octacarbonyl 、 十二/十四烷基二甲基氧化胺 作用下， 以 甲苯 为溶剂， 反应 11.5h， 以80%的产率得到(4S,5aR,6S,9aS,9bR)-4-[tert-butyl(dimethyl)silyl]oxy-7,9b-dimethyl-6-trimethylsilyloxy-4,5,5a,6,9,9a-hexahydro-1H-cyclopenta[a]naphthalen-2-one
  参考文献：
  名称：

  What Controls Stereoselectivity and Reactivity in the Synthesis of a trans-Decalin with a Quaternary Chiral Center via the Intramolecular Pauson–Khand Reaction: A Theoretical Study

  摘要：

  The Co-2(CO)(8)-mediated intramolecular PausonKhand reaction is an efficient approach to the trans-decalin subunit with a defined C1 quaternary chiral center. The newly developed density functional theory method M11-L was employed to study the mechanism, reactivity, and stereoselectivity for this reaction. The rate- and stereoselectivity-determining step is the intramolecular alkene insertion into the carboncobalt bond. Insertion of the alkene by the re- and si-face was studied to explain the stereoselectivity. The effects of varying the substituent on the acetylene and the C3 chirality were investigated experimentally and theoretically.

  DOI：

  10.1021/om500840q
• 作为产物：
  描述：

  2-((1R,2S,6S)-3-methyl-6-(prop-1-en-2-yl)-2-((trimethylsilyl)oxy)cyclohex-3-en-1-yl) acetaldehyde 在 咪唑 、 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.75h， 生成 tert-butyl-dimethyl-[(2S)-1-[(1R,2S,6S)-3-methyl-6-prop-1-en-2-yl-2-trimethylsilyloxycyclohex-3-en-1-yl]but-3-yn-2-yl]oxysilane
  参考文献：
  名称：

  Development of an expedient intramolecular Pauson–Khand reaction approach to stereoselectively construct the trans-decalin with a C1 quaternary chiral center

  摘要：

  通过Pauson-Khand反应（PKR）作为关键步骤，已经实现了具有明确定义的C1四元手性中心的反式去卡林亚基团的立体选择性合成。这种开发的化学方法为合成基于反式去卡林的生物活性天然产品提供了IMDA反应的替代方案。

  DOI：

  10.1039/c3cc45170d

文献信息

• Development of an expedient intramolecular Pauson–Khand reaction approach to stereoselectively construct the trans-decalin with a C1 quaternary chiral center
  作者：Li-Li Shi、Hong-Juan Shen、Li-Chao Fang、Jun Huang、Chuang-Chuang Li、Zhen Yang

  DOI：10.1039/c3cc45170d

  日期：——

  Stereoselective synthesis of the trans-decalin subunit with a defined C1 quaternary chiral center has been achieved by the Pauson–Khand reaction (PKR) as a key step. The developed chemistry offers an alternative to the IMDA reaction that has been used for the syntheses of trans-decalin based biologically active natural products.

  通过Pauson-Khand反应（PKR）作为关键步骤，已经实现了具有明确定义的C1四元手性中心的反式去卡林亚基团的立体选择性合成。这种开发的化学方法为合成基于反式去卡林的生物活性天然产品提供了IMDA反应的替代方案。
• What Controls Stereoselectivity and Reactivity in the Synthesis of a <i>trans</i>-Decalin with a Quaternary Chiral Center via the Intramolecular Pauson–Khand Reaction: A Theoretical Study
  作者：Song Liu、Hongjuan Shen、Zhaoyuan Yu、Lili Shi、Zhen Yang、Yu Lan

  DOI：10.1021/om500840q

  日期：2014.11.24

  The Co-2(CO)(8)-mediated intramolecular PausonKhand reaction is an efficient approach to the trans-decalin subunit with a defined C1 quaternary chiral center. The newly developed density functional theory method M11-L was employed to study the mechanism, reactivity, and stereoselectivity for this reaction. The rate- and stereoselectivity-determining step is the intramolecular alkene insertion into the carboncobalt bond. Insertion of the alkene by the re- and si-face was studied to explain the stereoselectivity. The effects of varying the substituent on the acetylene and the C3 chirality were investigated experimentally and theoretically.