(R,S)-pantoylnaphthylethylamine | 851984-42-4

• 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,S)-pantoylnaphthylethylamine
• 英文别名: pantoyl naphthylethylamine；(3S)-4,4-dimethyl-3-[[(1R)-1-naphthalen-1-ylethyl]amino]oxolan-2-one
• CAS: 851984-42-4
• 化学式: C₁₈H₂₁NO₂
• 分子量: 283.37
• InChiKey: NMVPVWIMIUAIDC-MLGOLLRUSA-N

物化性质

• 沸点：
  457.0±38.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R,S)-pantoylnaphthylethylamine 在 palladium 10% on activated carbon 、 氢气 作用下， 以 甲醇 为溶剂， 20.0 ℃ 、1.0 MPa 条件下， 反应 14.0h， 以91%的产率得到(S)-amino-4,4-dimethyldihydrofuran-2-one
  参考文献：
  名称：

  Aminolactone Chiral Modifiers for Heterogeneous Asymmetric Hydrogenation: Corrected Structure of Pantoyl-Naphthylethylamine, In-Situ Hydrogenolysis, and Scanning Tunneling Microscopy Observation of Supramolecular Aminolactone/Substrate Assemblies on Pt(111)

  摘要：

  As established by Balker and co-workers, pantoylnaphthylethylamine (PNEA) is an efficient synthetic chiral modifier for the asymmetric hydrogenation of ketopantolactone (KPL) to pantolactone on supported Pt catalysts. We report a scanning tunneling microscopy (STM) study of PNEA and PNEA-derived aminolactone species on Pt(111) and a reassignment of the relative stereochemistry of the modifier. Robust organic chemistry methods were used to establish that the structure of PNEA is R,S rather than R,R. The dissociative chemisorption of a fraction of PNEA adsorbed on Pt(111) yields two fragments that we attribute to a process involving C-N bond scission. We show that C-N bond scission occurs under hydrogenation conditions on PNEA-modified Pt/Al2O3 catalysts, forming the aminolactone amino-4,4-dimethyldihydrofuran-2-one (AF). STM measurements on (S)-AF and 2,2,2-trifluoroacetophenone coadsorbed on Pt(111) show the formation of isolated 1:1 complexes. In contrast, measurements on coadsorbed (S)-AF and KPL show fluxional supramolecular AF/KPL assemblies. The possibility that such assemblies contribute to the overall enantioselectivity observed for PNEA-modified Pt catalysts is discussed.

  DOI：

  10.1021/cs4007588
• 作为产物：
  描述：

  二氢-4,4-二甲基-2,3-呋喃二酮 、 (R)-1-(1-萘基)乙胺 在 sodium cyanoborohydride 作用下， 以 乙醇 、 溶剂黄146 为溶剂， 反应 44.0h， 以13%的产率得到(R,S)-pantoylnaphthylethylamine
  参考文献：
  名称：

  基于1-（1-萘基）-乙胺的手性改性剂对Pt催化的非均相不对称氢化的吸附和稳定性†

  摘要：

  为了调节效率并扩展手性改性金属催化剂上不对称氢化的多功能性，非常需要适用于模块结构的合成手性改性剂。简单手性改性剂（R）-1-（1-萘基）-乙胺[（R）-NEA]和升级的仲胺手性改性剂（R，S）-泛酰基萘乙胺[（R，S）-PNEA]已在催化加氢条件下进行了研究。使用衰减全反射红外（ATR-IR）光谱，（R）-NEA和（R，S）-PNEA在技术含量为5 wt％的Pt / Al 2 O 3催化剂的固液界面处进行了研究。除萘基外，（R，S）-PNEA还通过其泛酰基部分锚定在Pt上，从而为酮基内酯（KPL）的不对称氢化提供了增强的锚定作用和更好的手性表面位点。讨论了影响基于NEA的手性改性剂稳定性的因素。最近发现的（R，S）-PNEA，（S）-氨基-4,4-二甲基-二氢呋喃-2-酮[（S）-AF]的手性片段化产物在赋予化合物对映选择性方面不起作用。 KPL不对称氢化。

  DOI：

  10.1039/c4cy01136h

文献信息

• Adsorption and stability of chiral modifiers based on 1-(1-naphthyl)-ethylamine for Pt catalysed heterogeneous asymmetric hydrogenations
  作者：Fabian Meemken、Titian Steiger、Mareike C. Holland、Ryan Gilmour、Konrad Hungerbühler、Alfons Baiker

  DOI：10.1039/c4cy01136h

  日期：——

  efficiency and extending the versatility of asymmetric hydrogenations on chirally-modified metal catalysts. Adsorptive anchoring and structural stability of the simple chiral modifier (R)-1-(1-naphthyl)-ethylamine [(R)-NEA] and the upgraded, secondary amine chiral modifier (R,S)-pantoylnaphthylethylamine [(R,S)-PNEA] have been investigated under catalytic hydrogenation conditions. Using attenuated total reflection-infrared

  为了调节效率并扩展手性改性金属催化剂上不对称氢化的多功能性，非常需要适用于模块结构的合成手性改性剂。简单手性改性剂（R）-1-（1-萘基）-乙胺[（R）-NEA]和升级的仲胺手性改性剂（R，S）-泛酰基萘乙胺[（R，S）-PNEA]已在催化加氢条件下进行了研究。使用衰减全反射红外（ATR-IR）光谱，（R）-NEA和（R，S）-PNEA在技术含量为5 wt％的Pt / Al 2 O 3催化剂的固液界面处进行了研究。除萘基外，（R，S）-PNEA还通过其泛酰基部分锚定在Pt上，从而为酮基内酯（KPL）的不对称氢化提供了增强的锚定作用和更好的手性表面位点。讨论了影响基于NEA的手性改性剂稳定性的因素。最近发现的（R，S）-PNEA，（S）-氨基-4,4-二甲基-二氢呋喃-2-酮[（S）-AF]的手性片段化产物在赋予化合物对映选择性方面不起作用。 KPL不对称氢化。
• Aminolactone Chiral Modifiers for Heterogeneous Asymmetric Hydrogenation: Corrected Structure of Pantoyl-Naphthylethylamine, In-Situ Hydrogenolysis, and Scanning Tunneling Microscopy Observation of Supramolecular Aminolactone/Substrate Assemblies on Pt(111)
  作者：Guillaume Goubert、Vincent Demers-Carpentier、Richard P. Loach、Raphaël Lafleur-Lambert、Jean-Christian Lemay、John Boukouvalas、Peter H. McBreen

  DOI：10.1021/cs4007588

  日期：2013.12.6

  As established by Balker and co-workers, pantoylnaphthylethylamine (PNEA) is an efficient synthetic chiral modifier for the asymmetric hydrogenation of ketopantolactone (KPL) to pantolactone on supported Pt catalysts. We report a scanning tunneling microscopy (STM) study of PNEA and PNEA-derived aminolactone species on Pt(111) and a reassignment of the relative stereochemistry of the modifier. Robust organic chemistry methods were used to establish that the structure of PNEA is R,S rather than R,R. The dissociative chemisorption of a fraction of PNEA adsorbed on Pt(111) yields two fragments that we attribute to a process involving C-N bond scission. We show that C-N bond scission occurs under hydrogenation conditions on PNEA-modified Pt/Al2O3 catalysts, forming the aminolactone amino-4,4-dimethyldihydrofuran-2-one (AF). STM measurements on (S)-AF and 2,2,2-trifluoroacetophenone coadsorbed on Pt(111) show the formation of isolated 1:1 complexes. In contrast, measurements on coadsorbed (S)-AF and KPL show fluxional supramolecular AF/KPL assemblies. The possibility that such assemblies contribute to the overall enantioselectivity observed for PNEA-modified Pt catalysts is discussed.