(R)-2-(benzylideneamino)-2-(2-chlorophenyl)acetamide | 138228-59-8

• 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: (R)-2-(benzylideneamino)-2-(2-chlorophenyl)acetamide
• 英文别名: 2-(benzylideneamino)-2-(2-chlorophenyl)acetamide；(2R)-2-(benzylideneamino)-2-(2-chlorophenyl)acetamide
• CAS: 138228-59-8
• 化学式: C₁₅H₁₃ClN₂O
• 分子量: 272.734
• InChiKey: QAPUGHQEJNBWPB-CQSZACIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-2-(benzylideneamino)-2-(2-chlorophenyl)acetamide 以 乙腈 为溶剂， 反应 0.83h， 生成 (S)-2-(benzylideneamino)-2-(2-chlorophenyl)acetamide
  参考文献：
  名称：

  Pasteur’s Tweezers Revisited: On the Mechanism of Attrition-Enhanced Deracemization and Resolution of Chiral Conglomerate Solids

  摘要：

  Insights into the mechanism of attrition-enhanced deracemization and resolution of solid enantiomorphic chiral compounds are obtained by crystal size and solubility measurements and by isotopic labeling experiments. Together these results help to deconvolute the various chemical and physical rate processes contributing to the phenomenon. Crystal size measurements highlight a distinct correlation between the stochastic, transient growth of crystals and the emergence of a single solid enantiomorph under attrition conditions. The rapid mass transfer of molecules between the solution and solid phases under attrition is demonstrated, and the concept of a crystal-size-induced solubility driving force is exploited to overcome the stochastic nature of the crystal growth and dissolution processes. Extension to non-racemizing conditions provides a novel methodology for chiral resolution. Implications both for practical chiral separations and for the origin of biological homochirality are discussed.

  DOI：

  10.1021/ja303566g
• 作为产物：
  描述：

  2-氨基-2-(2-氯苯基)乙酸甲酯 在 ammonium hydroxide 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 生成 (R)-2-(benzylideneamino)-2-(2-chlorophenyl)acetamide
  参考文献：
  名称：

  Pasteur’s Tweezers Revisited: On the Mechanism of Attrition-Enhanced Deracemization and Resolution of Chiral Conglomerate Solids

  摘要：

  Insights into the mechanism of attrition-enhanced deracemization and resolution of solid enantiomorphic chiral compounds are obtained by crystal size and solubility measurements and by isotopic labeling experiments. Together these results help to deconvolute the various chemical and physical rate processes contributing to the phenomenon. Crystal size measurements highlight a distinct correlation between the stochastic, transient growth of crystals and the emergence of a single solid enantiomorph under attrition conditions. The rapid mass transfer of molecules between the solution and solid phases under attrition is demonstrated, and the concept of a crystal-size-induced solubility driving force is exploited to overcome the stochastic nature of the crystal growth and dissolution processes. Extension to non-racemizing conditions provides a novel methodology for chiral resolution. Implications both for practical chiral separations and for the origin of biological homochirality are discussed.

  DOI：

  10.1021/ja303566g

文献信息

• Isotopically Directed Symmetry Breaking and Enantioenrichment in Attrition-Enhanced Deracemization
  作者：James I. Murray、Jacob N. Sanders、Paul F. Richardson、K. N. Houk、Donna G. Blackmond

  DOI：10.1021/jacs.9b11422

  日期：2020.2.26

  The evolution of homochirality via attrition-enhanced deracemization (AED) of enantiomorphic solids is carried out using molecules that differ only in the isotopic composition of a phenyl group positioned remote from the chiral center. Enantioenrichment consistently favors the enantiomorph containing a deuterated phenyl group over the protio or C-13 version, and the protio version is consistently favored over the C-13 version. While these isotopic compounds exhibit identical crystal structures and solubilities, the trend in deracemization correlates with melting points. Understanding the origin of this isotope bias provides fundamental clues about overcoming stochastic behavior to direct the stereochemical outcome in attrition-enhanced deracemization processes. The energy required for breaking symmetry with chiral bias is compared for this near-equilibrium AED process and the far-from-equilibrium Soai autocatalytic reaction. Implications for the origin of biological homochirality are discussed.
• Pasteur’s Tweezers Revisited: On the Mechanism of Attrition-Enhanced Deracemization and Resolution of Chiral Conglomerate Solids
  作者：Jason E. Hein、Blessing Huynh Cao、Cristobal Viedma、Richard M. Kellogg、Donna G. Blackmond

  DOI：10.1021/ja303566g

  日期：2012.8.1

  Insights into the mechanism of attrition-enhanced deracemization and resolution of solid enantiomorphic chiral compounds are obtained by crystal size and solubility measurements and by isotopic labeling experiments. Together these results help to deconvolute the various chemical and physical rate processes contributing to the phenomenon. Crystal size measurements highlight a distinct correlation between the stochastic, transient growth of crystals and the emergence of a single solid enantiomorph under attrition conditions. The rapid mass transfer of molecules between the solution and solid phases under attrition is demonstrated, and the concept of a crystal-size-induced solubility driving force is exploited to overcome the stochastic nature of the crystal growth and dissolution processes. Extension to non-racemizing conditions provides a novel methodology for chiral resolution. Implications both for practical chiral separations and for the origin of biological homochirality are discussed.