(1S,2R,4S)-N-(tert-butoxycarbonyl)-2-hydroxy-1-hydroxymethyl-7-azabicyclo[2.2.1]heptane | 449171-49-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (1S,2R,4S)-N-(tert-butoxycarbonyl)-2-hydroxy-1-hydroxymethyl-7-azabicyclo[2.2.1]heptane
• 英文别名: tert-butyl (1S,2R,4S)-2-hydroxy-1-(hydroxymethyl)-7-azabicyclo[2.2.1]heptane-7-carboxylate
• CAS: 449171-49-7
• 化学式: C₁₂H₂₁NO₄
• 分子量: 243.303
• InChiKey: OQJVGUITYJXCPG-SBMIAAHKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.88
• 重原子数：
  17.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  70.0
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  methyl (1R,2R,4S)-N-(tert-butoxycarbonyl)-2-hydroxy-7-azabicyclo[2.2.1]heptane-1-carboxylate 在 sodium tetrahydroborate 、 cerium(III) chloride 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 3.0h， 以90%的产率得到(1S,2R,4S)-N-(tert-butoxycarbonyl)-2-hydroxy-1-hydroxymethyl-7-azabicyclo[2.2.1]heptane
  参考文献：
  名称：

  3-羟基脯氨酸对映体类似物及其衍生物的合成

  摘要：

  描述了所有四个对映体纯的2-羟基-7-氮杂双环[2.2.1]庚烷-1-甲酸，它们是3-羟基脯氨酸的新型限制性类似物。合成从2-苯甲酰胺基丙烯酸甲酯和Danishefsky's二烯之间的Diels-Alder反应开始，并将关键步骤用于环己烷环中甲磺酸酯基团的碱促进的内部亲核取代，然后采用拆分方法，该方法涉及非对映异构体的形成和进一步的形成。通过结晶分离。这种合成途径使我们能够获得N -Boc-7-氮杂双环[2.2.1]庚烷-2-酮的对映异构体，用作（-）-和（+）-依巴替丁的前体的有价值的酮以及其他更有趣的类似物。

  DOI：

  10.1016/s0957-4166(02)00158-1