ethyl (2E,4E)-6-[(tert-butyldiphenylsilyl)oxy]-2-fluoro-4-methylhexa-2,4-dienoate | 186953-24-2

• 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: ethyl (2E,4E)-6-[(tert-butyldiphenylsilyl)oxy]-2-fluoro-4-methylhexa-2,4-dienoate
• 英文别名: ethyl (2E,4E)-6-[tert-butyl(diphenyl)silyl]oxy-2-fluoro-4-methylhexa-2,4-dienoate
• CAS: 186953-24-2
• 化学式: C₂₅H₃₁FO₃Si
• 分子量: 426.603
• InChiKey: CNGXWJDZPQCPFC-VJMDKUEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.93
• 重原子数：
  30
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl (2E,4E)-6-[(tert-butyldiphenylsilyl)oxy]-2-fluoro-4-methylhexa-2,4-dienoate 在 manganese(IV) oxide 、 正丁基锂 、 barium permanganate 、 四丁基氟化铵 、 二异丁基氢化铝 、 sodium carbonate 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 22.0h， 生成 11-cis-11-fluororetinal
  参考文献：
  名称：

  Synthesis of Retinals Fluorinated at Odd-Numbered Side-Chain Positions and of the Corresponding Fluorobacteriorhodopsins

  摘要：

  Conventional Horner-Wadsworth-Emmons and Wittig condensations were used to fluorinate the odd-numbered positions of the retinal side chain past C-7. The stereochemically labile cis-fluororetinals were easily converted into the most stable trans-flouretinals, which were incubated with bacterio-opsin. Contrary to expectations, the fluorinated retinals provided artificial pigments with near normal absorption properties, showing that any electrostatic interactions between the fluorine atoms and protein groups were insufficient to prevent normal binding. The new artificial pigments had smaller opsin shifts than did native bacteriorhodopsin, which is interpreted as due either to greater electrostatic interaction between the protonated imine and its counterion, or to local interactions between the fluorine substituents and nearby polar protein groups.

  DOI：

  10.1021/jo961355x
• 作为产物：
  描述：

  2-氟-2-磷酰基乙酸三乙酯 、 (E)-4-((tert-butyldiphenylsilyl)oxy)-2-methylbut-2-enal 在 正丁基锂 作用下， 生成 ethyl (2E,4E)-6-[(tert-butyldiphenylsilyl)oxy]-2-fluoro-4-methylhexa-2,4-dienoate
  参考文献：
  名称：

  Synthesis of Retinals Fluorinated at Odd-Numbered Side-Chain Positions and of the Corresponding Fluorobacteriorhodopsins

  摘要：

  Conventional Horner-Wadsworth-Emmons and Wittig condensations were used to fluorinate the odd-numbered positions of the retinal side chain past C-7. The stereochemically labile cis-fluororetinals were easily converted into the most stable trans-flouretinals, which were incubated with bacterio-opsin. Contrary to expectations, the fluorinated retinals provided artificial pigments with near normal absorption properties, showing that any electrostatic interactions between the fluorine atoms and protein groups were insufficient to prevent normal binding. The new artificial pigments had smaller opsin shifts than did native bacteriorhodopsin, which is interpreted as due either to greater electrostatic interaction between the protonated imine and its counterion, or to local interactions between the fluorine substituents and nearby polar protein groups.

  DOI：

  10.1021/jo961355x

文献信息

• Synthesis of Retinals Fluorinated at Odd-Numbered Side-Chain Positions and of the Corresponding Fluorobacteriorhodopsins
  作者：Andrés Francesch、Rosana Alvarez、Susana López、Angel R. de Lera

  DOI：10.1021/jo961355x

  日期：1997.1.1

  Conventional Horner-Wadsworth-Emmons and Wittig condensations were used to fluorinate the odd-numbered positions of the retinal side chain past C-7. The stereochemically labile cis-fluororetinals were easily converted into the most stable trans-flouretinals, which were incubated with bacterio-opsin. Contrary to expectations, the fluorinated retinals provided artificial pigments with near normal absorption properties, showing that any electrostatic interactions between the fluorine atoms and protein groups were insufficient to prevent normal binding. The new artificial pigments had smaller opsin shifts than did native bacteriorhodopsin, which is interpreted as due either to greater electrostatic interaction between the protonated imine and its counterion, or to local interactions between the fluorine substituents and nearby polar protein groups.