(2'S,4R,5S)-3-(2'-methyl-3'-phenylpropionyl)-4-methyl-5-phenyloxazolidin-2-one | 80697-94-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2'S,4R,5S)-3-(2'-methyl-3'-phenylpropionyl)-4-methyl-5-phenyloxazolidin-2-one
• 英文别名: (4R,5S)-4-methyl-3-((S)-2-methyl-3-phenylpropanoyl)-5-phenyloxazolidin-2-one；(4R,5S)-4-methyl-3-[(2S)-2-methyl-3-phenylpropanoyl]-5-phenyl-1,3-oxazolidin-2-one
• CAS: 80697-94-5
• 化学式: C₂₀H₂₁NO₃
• 分子量: 323.392
• InChiKey: JWJABRJKLSRJIA-HDMKZQKVSA-N

物化性质

• 沸点：
  503.8±49.0 °C(Predicted)
• 密度：
  1.168±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-叔丁基丙烯酰胺 、 (2'S,4R,5S)-3-(2'-methyl-3'-phenylpropionyl)-4-methyl-5-phenyloxazolidin-2-one 在 samarium diiodide 、 水 、 盐酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 25.0h， 以72%的产率得到(S)-N-tert-butyl-5-methyl-4-oxo-6-phenylhexanamide
  参考文献：
  名称：

  SmI 2促进与手性N-酰基恶唑烷酮的分子内和分子间CC键形成

  摘要：

  在分子间和分子内反应中，研究了手性恶唑烷酮在N-酰基恶唑烷酮单元的酰亚胺官能团和烯烃自由基受体之间的SmI 2介导的CC键生成中的适用性。结果表明，埃文斯不对称烷基化反应的产物可以与丙烯酰胺直接形成碳-碳键，从而以合理的收率提供手性无环酮。这些实施例代表了这种N-酰基恶唑烷酮的第一次转化，其中该手性助剂在形成酮的条件下被除去。5- exo - trig环化研究也使用相同类型的底物进行，提供了反式-2，5-二取代的环戊酮的产率约为 50％。但是，尝试环化含杂原子的等价物的回报较小。

  DOI：

  10.1016/j.tet.2008.09.044
• 作为产物：
  描述：

  DL-苯丙醇胺盐酸盐 在 正丁基锂 、 sodium hexamethyldisilazane 、 potassium carbonate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 7.17h， 生成 (2'S,4R,5S)-3-(2'-methyl-3'-phenylpropionyl)-4-methyl-5-phenyloxazolidin-2-one
  参考文献：
  名称：

  The preparation and reaction of enolates within micro reactors

  摘要：

  Over the past 5 years, interest in the miniaturisation of chemical synthesis has grown rapidly, however in order to facilitate transfer of the technology from its current position as a research tool to industrial applications, a core understanding of the challenges associated with transferring reactions from the macro to the micro domain is required. This paper therefore aims to broach this problem by investigating the application of micro reactors to a range of commonly employed synthetic reactions including acylation, aldol, alkylation, 1,4-conjugate addition (Michael addition) and the Knoevenagel condensation. Comparison of the results obtained with traditional batch techniques enable us to highlight some of the advantages associated with micro reaction technology. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.08.076

文献信息

• Importance of C−N Bond Rotation in <i>N</i>-Acyl Oxazolidinones in their SmI₂-Promoted Coupling to Acrylamides
  作者：Rolf H. Taaning、Karl B. Lindsay、Birgit Schiøtt、Kim Daasbjerg、Troels Skrydstrup

  DOI：10.1021/ja903401y

  日期：2009.7.29

  correlates with the activation barriers for C-N bond rotation may have implications for other useful synthetic organic reactions involving similar substrates. Finally, these studies were extrapolated to understanding the poor reactivity of N-acyl oxazolidinones, as those derived from Evans chiral auxiliaries, with N-tert-butyl acrylamide. These couplings appear to be dominated by the activation energy for addition

  进行了详细的机理研究，以确定 SmI(2) 促进的 N-酰基恶唑烷酮和丙烯酰胺之间的碳-碳键形成反应中后电子转移步骤的主要因素。通过使两种 N-酰基恶唑烷酮与有限量的 N-叔丁基丙烯酰胺反应来进行竞争实验，然后根据产物分布，计算一系列 N-酰基恶唑烷酮对 N-新戊酰基恶唑烷酮的相对反应性值 (RV)作为参考。当 ln RV 与通过 DFT 计算获得的 CN 键旋转（s-反式到 s-顺式）的激活势垒作图时，对于简单的烷基 N-酰基恶唑烷酮获得了几乎线性的相关性，这意味着 CN 键从 s-trans 到 s-cis 构象的旋转是控制反应性的基本参数之一。这些结果得到了对相应酰亚胺衍生物进行的其他竞争实验的证实，其中旋转对于获得双齿配位是不必要的，并且没有观察到上述的这种相关性。对这些 SmI(2) 介导的转化的简单 N-酰基恶唑烷酮的反应性与 CN 键旋转的激活障碍相关的发现可能对涉及类似底物
• Hydrogenation of N-Acylcarbamates and N-Acylsulfonamides Catalyzed by a Bifunctional [Cp*Ru(PN)] Complex
  作者：Masato Ito、Lee Wei Koo、Akio Himizu、Chika Kobayashi、Ayaka Sakaguchi、Takao Ikariya

  DOI：10.1002/anie.200805307

  日期：2009.2.2

  Awakening of the Cp one: The bifunctional complex 1 facilitates the interaction with substrates bearing less electrophilic carbon atoms than ketones, epoxides, and imides. The title reaction was applicable to the reduction of Evans' asymmetric alkylation products to the chiral alcohols along with good recovery of the chiral oxazolidinone auxiliary. EWG=electron‐withdrawing group.

  Cp 1的唤醒：双功能配合物1促进了与具有比酮，环氧化物和酰亚胺少的亲电子碳原子的底物的相互作用。该标题反应适用于将埃文斯的不对称烷基化产物还原为手性醇，以及良好的手性恶唑烷酮助剂的回收率。EWG =吸电子基团。
• Asymmetric alkylation reactions of chiral imide enolates. A practical approach to the enantioselective synthesis of .alpha.-substituted carboxylic acid derivatives
  作者：D. A. Evans、M. D. Ennis、D. J. Mathre

  DOI：10.1021/ja00370a050

  日期：1982.3
• The preparation and reaction of enolates within micro reactors
  作者：Charlotte Wiles、Paul Watts、Stephen J. Haswell、Esteban Pombo-Villar

  DOI：10.1016/j.tet.2005.08.076

  日期：2005.11

  Over the past 5 years, interest in the miniaturisation of chemical synthesis has grown rapidly, however in order to facilitate transfer of the technology from its current position as a research tool to industrial applications, a core understanding of the challenges associated with transferring reactions from the macro to the micro domain is required. This paper therefore aims to broach this problem by investigating the application of micro reactors to a range of commonly employed synthetic reactions including acylation, aldol, alkylation, 1,4-conjugate addition (Michael addition) and the Knoevenagel condensation. Comparison of the results obtained with traditional batch techniques enable us to highlight some of the advantages associated with micro reaction technology. (c) 2005 Elsevier Ltd. All rights reserved.
• SmI2-promoted intra- and intermolecular C–C bond formation with chiral N-acyl oxazolidinones
  作者：Rolf H. Taaning、Laura Thim、Jacob Karaffa、Araceli G. Campaña、Anna-Mette Hansen、Troels Skrydstrup

  DOI：10.1016/j.tet.2008.09.044

  日期：2008.12

  The suitability of chiral oxazolidinones in the SmI2-mediated C–C bond generation between the imide functionality of an N-acyl oxazolidinone unit and an olefinic radical acceptor, in both inter- and intramolecular reactions, was investigated. It was shown that the products from an Evans asymmetric alkylation can undergo direct carbon–carbon bond formation with an acrylamide providing chiral acyclic

  在分子间和分子内反应中，研究了手性恶唑烷酮在N-酰基恶唑烷酮单元的酰亚胺官能团和烯烃自由基受体之间的SmI 2介导的CC键生成中的适用性。结果表明，埃文斯不对称烷基化反应的产物可以与丙烯酰胺直接形成碳-碳键，从而以合理的收率提供手性无环酮。这些实施例代表了这种N-酰基恶唑烷酮的第一次转化，其中该手性助剂在形成酮的条件下被除去。5- exo - trig环化研究也使用相同类型的底物进行，提供了反式-2，5-二取代的环戊酮的产率约为 50％。但是，尝试环化含杂原子的等价物的回报较小。