| 1609952-44-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪烷类
• CAS: 1609952-44-4
• 化学式: C₁₉H₃₅NO₃Si
• 分子量: 353.577
• InChiKey: BINJWFPOCMATKR-KXBFYZLASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.11
• 重原子数：
  24.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  38.77
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  在 Amberlyst 15 作用下， 以 甲醇 为溶剂， 反应 2.5h， 以95%的产率得到
  参考文献：
  名称：

  Robust trans-Amide Helical Structure of Oligomers of Bicyclic Mimics of β-Proline: Impact of Positional Switching of Bridgehead Substituent on Amide cis–trans Equilibrium

  摘要：

  Because homooligomers of 7-azabicyclo [2.2.1]-heptane-2-endo-carboxylic acid, a bridged beta-proline analogue with a substituent installed at the remote C4-bridgehead position, completely biased the amide cis-trans equilibrium to the cis-amide structure, we expected that introduction of a substituent at the C1-bridgehead position adjacent to the carboxylic acid moiety, rather than the remote C4-bridgehead position, would tip the cis trans amide equilibrium toward trans-amide structure without the aid of hydrogen bonding. Thus, in this work we established an efficient synthetic route to an optically active bicyclic analogue of 1,1-disubstituted beta-proline, bearing a substituent at the C1-bridgehead position. Crystallographic, spectroscopic, and computational studies showed that indeed oligomers of this analogue take a consistent helical structure involving all-trans-amide linkages, independently of the number of residues, from the dimer up to the octamer. Oligomers composed of (R)-beta-amino acid units form an extended left-handed helix with about 2.7 residues per turn and an approximately 4.0 angstrom rise per residue, characterized by complete lack of main-chain hydrogen bonding. This unique helical structure shows some similarity in shape to the trans-amide-based polyproline II (PPII) helix. The present helix was stable in various kinds of solvents such as alcohols. The present work provided a fundamental structural basis for future applications.

  DOI：

  10.1021/jo500916j
• 作为产物：
  描述：

  (1S,2R,4S)-N-(tert-butoxycarbonyl)-2-hydroxy-1-hydroxymethyl-7-azabicyclo[2.2.1]heptane 在 4-二甲氨基吡啶 、 草酰氯 、 potassium tert-butylate 、 甲基三苯基溴化膦 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 21.92h， 生成
  参考文献：
  名称：

  Robust trans-Amide Helical Structure of Oligomers of Bicyclic Mimics of β-Proline: Impact of Positional Switching of Bridgehead Substituent on Amide cis–trans Equilibrium

  摘要：

  Because homooligomers of 7-azabicyclo [2.2.1]-heptane-2-endo-carboxylic acid, a bridged beta-proline analogue with a substituent installed at the remote C4-bridgehead position, completely biased the amide cis-trans equilibrium to the cis-amide structure, we expected that introduction of a substituent at the C1-bridgehead position adjacent to the carboxylic acid moiety, rather than the remote C4-bridgehead position, would tip the cis trans amide equilibrium toward trans-amide structure without the aid of hydrogen bonding. Thus, in this work we established an efficient synthetic route to an optically active bicyclic analogue of 1,1-disubstituted beta-proline, bearing a substituent at the C1-bridgehead position. Crystallographic, spectroscopic, and computational studies showed that indeed oligomers of this analogue take a consistent helical structure involving all-trans-amide linkages, independently of the number of residues, from the dimer up to the octamer. Oligomers composed of (R)-beta-amino acid units form an extended left-handed helix with about 2.7 residues per turn and an approximately 4.0 angstrom rise per residue, characterized by complete lack of main-chain hydrogen bonding. This unique helical structure shows some similarity in shape to the trans-amide-based polyproline II (PPII) helix. The present helix was stable in various kinds of solvents such as alcohols. The present work provided a fundamental structural basis for future applications.

  DOI：

  10.1021/jo500916j