ethyl 1-hydroxy-5-methoxy-2-(2,2,2-trifluoroacetamido)-1-cyclopropyl-2,3-dihydro-1H-indene-2-carboxylate | 1235574-99-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl 1-hydroxy-5-methoxy-2-(2,2,2-trifluoroacetamido)-1-cyclopropyl-2,3-dihydro-1H-indene-2-carboxylate
• 英文别名: 1-Hydroxy-1-cyclopropyl-2-(trifluoroacetylamino)-5-methoxy-2,3-dihydro-1H-indene-2-carboxylic acid ethyl ester；ethyl 3-cyclopropyl-3-hydroxy-6-methoxy-2-[(2,2,2-trifluoroacetyl)amino]-1H-indene-2-carboxylate
• CAS: 1235574-99-8
• 化学式: C₁₈H₂₀F₃NO₅
• 分子量: 387.356
• InChiKey: HBTFMWXMIWMNQF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  84.9
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  ethyl 1-hydroxy-5-methoxy-2-(2,2,2-trifluoroacetamido)-1-cyclopropyl-2,3-dihydro-1H-indene-2-carboxylate 在 三氟甲磺酸酐 作用下， 以 苯 为溶剂， 反应 0.5h， 生成 ethyl 6-methoxy-3-(1-methyl-5-phenyl-2,3-dihydropyrrol-1-ium-4-ylidene)-2-[(2,2,2-trifluoroacetyl)amino]-1H-indene-2-carboxylate;trifluoromethanesulfonate
  参考文献：
  名称：

  Toward a Stable α-Cycloalkyl Amino Acid with a Photoswitchable Cationic Side Chain

  摘要：

  The N-alkylated indanylidenepyrroline (NAIP) Schiff base 3 is an unnatural a-amino acid precursor potentially useful for the preparation of semisynthetic peptides and proteins incorporating charged side chains whose structure can be modulated via Z/E photoisomerization. Here we report that the heteroallylic protons of 3 led to partial loss of ethanol accompanied by formation of the novel heterocyclic system 4 during attempted deprotection. We also show that the same protons catalyze the thermal isomerization of 3, making the light-driven conformational control concept ineffective for times longer than a few hours. These problems are not present in the previously unreported compound 5 where the acidic methyl group is replaced by an H atom. Therefore, 5, rather than 3, constitutes a promising prototype for the design of building blocks capable to modulate the electrostatic potential of a protein in specific locations via light irradiation.

  DOI：

  10.1021/jo2022263
• 作为产物：
  描述：

  ethyl 5-methoxy-1-oxo-2,3-dihydro-1H-indene-2-carboxylate 在 N-溴代丁二酰亚胺(NBS) 、 sodium azide 、 三苯基膦 作用下， 以 四氢呋喃 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 生成 ethyl 1-hydroxy-5-methoxy-2-(2,2,2-trifluoroacetamido)-1-cyclopropyl-2,3-dihydro-1H-indene-2-carboxylate
  参考文献：
  名称：

  Toward a Stable α-Cycloalkyl Amino Acid with a Photoswitchable Cationic Side Chain

  摘要：

  The N-alkylated indanylidenepyrroline (NAIP) Schiff base 3 is an unnatural a-amino acid precursor potentially useful for the preparation of semisynthetic peptides and proteins incorporating charged side chains whose structure can be modulated via Z/E photoisomerization. Here we report that the heteroallylic protons of 3 led to partial loss of ethanol accompanied by formation of the novel heterocyclic system 4 during attempted deprotection. We also show that the same protons catalyze the thermal isomerization of 3, making the light-driven conformational control concept ineffective for times longer than a few hours. These problems are not present in the previously unreported compound 5 where the acidic methyl group is replaced by an H atom. Therefore, 5, rather than 3, constitutes a promising prototype for the design of building blocks capable to modulate the electrostatic potential of a protein in specific locations via light irradiation.

  DOI：

  10.1021/jo2022263

文献信息

• Modeling, Preparation, and Characterization of a Dipole Moment Switch Driven by <i>Z</i>/<i>E</i> Photoisomerization
  作者：Alfonso Melloni、Riccardo Rossi Paccani、Donato Donati、Vinicio Zanirato、Adalgisa Sinicropi、Maria Laura Parisi、Elena Martin、Mikhail Ryazantsev、Wan Jian Ding、Luis Manuel Frutos、Riccardo Basosi、Stefania Fusi、Loredana Latterini、Nicolas Ferré、Massimo Olivucci

  DOI：10.1021/ja906733q

  日期：2010.7.14

  We report the results of a multidisciplinary research effort where the methods of computational photochemistry and retrosynthetic analysis/synthesis have contributed to the preparation of a novel N-alkylated indanylidene-pyrroline Schiff base featuring an exocyclic double bond and a permanent zwitterionic head. We show that, due to its large dipole moment and efficient photoisomerization, such a system may constitute the prototype of a novel generation of electrostatic switches achieving a reversible light-induced dipole moment change on the order of 30 D. The modeling of a peptide fragment incorporating the zwitterionic head into a conformationally rigid side chain shows that the switch can effectively modulate the fluorescence of a tryptophan probe.