12-methyl-10-oxo-9-azatricyclo<6.2.2.0^4,12>dodecane | 142811-31-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: 12-methyl-10-oxo-9-azatricyclo<6.2.2.0^4,12>dodecane
• 英文别名: (1R,4S,8S,9R)-9-methyl-3-azatricyclo[6.2.2.04,9]dodecan-2-one
• CAS: 142811-31-2
• 化学式: C₁₂H₁₉NO
• 分子量: 193.289
• InChiKey: DNCSKEBSCIXBNI-FYLLDIAZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  12-methyl-10-oxo-9-azatricyclo<6.2.2.0^4,12>dodecane 在 盐酸 、 氯化亚砜 作用下， 反应 25.0h， 生成 methyl 8a-methyl-1-aminooctalin-7-carboxylate
  参考文献：
  名称：

  Design and synthesis of intramolecular ion-pairing cis-bicyclo[4.4.0]decane (cis-decalin) amino acids: conformation-based probes of electrostatic interactions in water

  摘要：

  The design strategy and synthesis of cis-bicyclo[4.4.0]decane (cis-decalin) derivatives as conformation-based probes of electrostatic interactions in H2O are described. The molecules were designed so that formation of an intramolecular electrostatic interaction occurs in only one of two low-energy conformers; hence, the conformational equilibrium of a given molecule is under control of the electrostatic interaction, which can be determined accurately with NMR studies. The structural definition inherent to the molecules will enable the thermodynamics and kinetics of solvent reorganization, which controls formation of electrostatic interactions in H2O, to be probed directly. The first probe, a cis-decalin amino acid designed to evaluate an intramolecular ion pair, has been synthesized. The total synthesis was efficient and illustrated many of the strategies and potential pitfalls associated with the preparation of conformationally flexible ring systems. In particular, the inherent facial selectivity afforded by the shape of the cis-decalin, a critical component of the synthetic design, was reversed in one step in which hydrogen was added from the sterically encumbered concave face of the molecule. A cis-decalin amino acid of a different stereoelectronic array was also prepared. These molecules are the first examples to emerge from the application of a general design and synthetic strategy that will enable probes for all of the important biological electrostatic interactions to be constructed. The study of these molecules will provide significant insight into the synergistic role of molecular structure and solvent at controlling electrostatic interactions in H2O, an important basis of biological structure and function.

  DOI：

  10.1021/jo00042a015
• 作为产物：
  描述：

  methyl 8a-methyl-1-aminooctalin-7-carboxylate hydrochloride 在 sodium hydroxide 作用下， 生成 12-methyl-10-oxo-9-azatricyclo<6.2.2.0^4,12>dodecane
  参考文献：
  名称：

  Design and synthesis of intramolecular ion-pairing cis-bicyclo[4.4.0]decane (cis-decalin) amino acids: conformation-based probes of electrostatic interactions in water

  摘要：

  The design strategy and synthesis of cis-bicyclo[4.4.0]decane (cis-decalin) derivatives as conformation-based probes of electrostatic interactions in H2O are described. The molecules were designed so that formation of an intramolecular electrostatic interaction occurs in only one of two low-energy conformers; hence, the conformational equilibrium of a given molecule is under control of the electrostatic interaction, which can be determined accurately with NMR studies. The structural definition inherent to the molecules will enable the thermodynamics and kinetics of solvent reorganization, which controls formation of electrostatic interactions in H2O, to be probed directly. The first probe, a cis-decalin amino acid designed to evaluate an intramolecular ion pair, has been synthesized. The total synthesis was efficient and illustrated many of the strategies and potential pitfalls associated with the preparation of conformationally flexible ring systems. In particular, the inherent facial selectivity afforded by the shape of the cis-decalin, a critical component of the synthetic design, was reversed in one step in which hydrogen was added from the sterically encumbered concave face of the molecule. A cis-decalin amino acid of a different stereoelectronic array was also prepared. These molecules are the first examples to emerge from the application of a general design and synthetic strategy that will enable probes for all of the important biological electrostatic interactions to be constructed. The study of these molecules will provide significant insight into the synergistic role of molecular structure and solvent at controlling electrostatic interactions in H2O, an important basis of biological structure and function.

  DOI：

  10.1021/jo00042a015

文献信息

• Thermodynamic description of a contact and solvent-separated ion pair as a function of solvation: a model for salt bridges and proton-transfer reactions in biology
  作者：Craig Beeson、Thomas A. Dix

  DOI：10.1021/ja00075a049

  日期：1993.11

  evaluated, mimicked ion pairs found in biomolecules («salt bridges»). Conformational and transfer equilibria were evaluated from changes in 1 H NMR coupling constants and chemical shifts, respect the ion pair ΔGs could be extracted directly. Correlations of ion pair ΔGs with solvent polarity scales (E T (30) values) and solvent hydrogen bond acidities demonstrated the importance of stabilizing the carboxylate

  1α-氨基-8aβ-甲基双环[4.4.0]癸烷-7α-羧酸（1）的无溶剂化能量，一种顺式十氢化萘氨基酸，填充两个构象异构体，其中形成分子内接触或溶剂分离的离子对, 已在多种溶剂 (CDCl 3 至 D 2 O) 中测定。离子对的性质和评估的条件范围模拟了生物分子中发现的离子对（“盐桥”）。从 1 H NMR 耦合常数和化学位移的变化评估构象和转移平衡，考虑到离子对 ΔGs 可以直接提取。离子对 ΔGs 与溶剂极性标度（ET (30) 值）和溶剂氢键酸度的相关性证明了在低极性溶剂中稳定羧酸根离子的重要性