(S)-3-(1-naphthoyl)-4-isopropyl-2,2-dimethyloxazolidin-5-one | 1007599-18-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (S)-3-(1-naphthoyl)-4-isopropyl-2,2-dimethyloxazolidin-5-one
• 英文别名: (S)-4-isopropyl-2,2-dimethyl-3-(1-naphthoyl)oxazolidin-5-one；(4S)-2,2-dimethyl-3-(naphthalene-1-carbonyl)-4-(propan-2-yl)-1,3-oxazolidin-5-one；(4S)-2,2-dimethyl-3-(naphthalene-1-carbonyl)-4-propan-2-yl-1,3-oxazolidin-5-one
• CAS: 1007599-18-9
• 化学式: C₁₉H₂₁NO₃
• 分子量: 311.381
• InChiKey: AUUTUFIWMACFKD-INIZCTEOSA-N

物化性质

• 熔点：
  112 °C
• 沸点：
  507.5±43.0 °C(Predicted)
• 密度：
  1.157±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 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：

  (S)-3-(1-naphthoyl)-4-isopropyl-2,2-dimethyloxazolidin-5-one 在 双(三甲基硅烷基)氨基钾 、 氘代叔丁醇 作用下， 以 乙二醇二甲醚 、 乙醚 为溶剂， 反应 0.3h， 以76%的产率得到(S)-4-isopropyl-2,2-dimethyl-3-(1-naphthoyl)oxazolidin-5-one-4-d1
  参考文献：
  名称：

  叔芳酰胺手性记忆：一种简单有效的季α-氨基酸对映选择性合成方法

  摘要：

  已经开发了一种使用手性记忆不对称合成四元 α 取代氨基酸的新方法。该策略利用叔芳香酰胺的动态轴向手性来记住烯醇化步骤中α-氨基酸的初始手性。从五种不同的l-氨基酸开始，一步合成含有叔芳酰胺基团的相应恶唑烷-5-酮，然后用各种亲电子试剂进行烷基化，收率和对映选择性（高达96%，高达>99重结晶后的百分比）。一步脱保护提供对映体富集或对映体纯的季铵 α-氨基酸。我们在此描述了优化过程、在每个系列中获得的结果以及基于 NMR 研究的合理解释，DFT 计算和晶体结构。本文提出的方法构成了从叔l-氨基酸开始的对映纯季α-氨基酸的有效合成（仅三个步骤），没有任何外部手性来源。

  DOI：

  10.1021/ja9039604
• 作为产物：
  描述：

  (2S)-2-氨基-3-甲基丁酸钠 、 1-萘甲酰氯 在 4 A molecular sieve 、 三氟化硼乙醚 作用下， 以 丙酮 为溶剂， 反应 17.1h， 以73%的产率得到(S)-3-(1-naphthoyl)-4-isopropyl-2,2-dimethyloxazolidin-5-one
  参考文献：
  名称：

  Accurate conformation analysis in solution: NMR and DFT/PCM study of the S-3-(1-naphthoyl)-4-isopropyl-2,2-dimethyloxazolidin-5-one in CDCl3

  摘要：

  The title molecule has been synthesised and the low temperature NMR spectrum recorded in CDCl3. The spectrum shows that four conformers lie within 0.08 eV at 210 K. We show that an accurate conformation analysis can be obtained with a full and consistent use of the DFT (B3LYP) and PCM methods. If the polarised Stuttgart-Dresden basis and a PCM cavity with individual spheres on the hydrogen atoms are used, if the thermal and PCM non-electrostatic contributions are taken into account, and if a demanding convergence is achieved, then the rms error on the energy differences amounts to 0.002 eV. The 6-31 +g(d) basis is larger and yields a larger rms error: 0.006 eV. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.12.001

文献信息

• Highly Stereoselective Aldol Reactions by Memory of Chirality: Synthesis of Quaternary β‐Hydroxy α‐Amino Acids
  作者：Loïc Roupnel、Régis Guillot、Didier Gori、Baby Viswambharan、Cyrille Kouklovsky、Valérie Alezra

  DOI：10.1002/hlca.202100127

  日期：2021.10

  We describe here an asymmetric aldol reaction based on the principle of Memory of Chirality. From α-amino acids such as leucine and methionine, we have synthesized in two steps quaternary α-amino acid derivatives with high diastereoselectivity and enantioselectivity, using the chirality of the initial α-amino acid as the only chirality source. Furthermore, we were able to determine the relative and

  我们在这里描述了基于手性记忆原理的不对称醛醇反应。从α-氨基酸如亮氨酸和甲硫氨酸，我们以初始α-氨基酸的手性作为唯一的手性来源，分两步合成了具有高非对映选择性和对映选择性的季α-氨基酸衍生物。此外，由于晶体结构，我们能够确定醛醇产物的相对和绝对构型，因此表明相对构型取决于所使用的醛。我们提出了立体选择性解释，并在酸性水解后获得了季 β-羟基 α-氨基酸。
• Tertiary Aromatic Amide for Memory of Chirality: Access to Enantioenriched α-Substituted Valine
  作者：Mathieu Branca、Didier Gori、Régis Guillot、Valérie Alezra、Cyrille Kouklovsky

  DOI：10.1021/ja801165z

  日期：2008.5.1

  A new methodology for the asymmetric synthesis of quaternary alpha-substituted amino acids using memory of chirality has been developed. This strategy employs dynamic axial chirality of tertiary aromatic amides to memorize the initial chirality of an alpha-amino acid during the enolization step. Starting from L-valine, an oxazolidin-5-one containing a tertiary aromatic amide was synthesized in one step and then alkylated with various electrophiles with good yield and enantioselectivity (up to 96%). Quaternary products can be obtained enantiomerically pure by recrystallization. One-step deprotection affords enantioenriched (S)-alpha-methyl valine (ee = 94%) or enantiopure (S)-alpha-isopropyl aspartic acid (ee >99%) in only three steps starting from L-valine.
• Memory of Chirality of Tertiary Aromatic Amides: A Simple and Efficient Method for the Enantioselective Synthesis of Quaternary α-Amino Acids
  作者：Mathieu Branca、Sébastien Pena、Régis Guillot、Didier Gori、Valérie Alezra、Cyrille Kouklovsky

  DOI：10.1021/ja9039604

  日期：2009.8.5

  A new methodology for the asymmetric synthesis of quaternary alpha-substituted amino acids using memory of chirality has been developed. The strategy utilizes the dynamic axial chirality of tertiary aromatic amides to memorize the initial chirality of an alpha-amino acid during an enolization step. Starting from five different l-amino acids, the corresponding oxazolidin-5-ones containing a tertiary

  已经开发了一种使用手性记忆不对称合成四元 α 取代氨基酸的新方法。该策略利用叔芳香酰胺的动态轴向手性来记住烯醇化步骤中α-氨基酸的初始手性。从五种不同的l-氨基酸开始，一步合成含有叔芳酰胺基团的相应恶唑烷-5-酮，然后用各种亲电子试剂进行烷基化，收率和对映选择性（高达96%，高达>99重结晶后的百分比）。一步脱保护提供对映体富集或对映体纯的季铵 α-氨基酸。我们在此描述了优化过程、在每个系列中获得的结果以及基于 NMR 研究的合理解释，DFT 计算和晶体结构。本文提出的方法构成了从叔l-氨基酸开始的对映纯季α-氨基酸的有效合成（仅三个步骤），没有任何外部手性来源。
• Accurate conformation analysis in solution: NMR and DFT/PCM study of the S-3-(1-naphthoyl)-4-isopropyl-2,2-dimethyloxazolidin-5-one in CDCl3
  作者：Mathieu Branca、Valérie Alezra、Cyrille Kouklovsky、Pierre Archirel

  DOI：10.1016/j.tet.2007.12.001

  日期：2008.2

  The title molecule has been synthesised and the low temperature NMR spectrum recorded in CDCl3. The spectrum shows that four conformers lie within 0.08 eV at 210 K. We show that an accurate conformation analysis can be obtained with a full and consistent use of the DFT (B3LYP) and PCM methods. If the polarised Stuttgart-Dresden basis and a PCM cavity with individual spheres on the hydrogen atoms are used, if the thermal and PCM non-electrostatic contributions are taken into account, and if a demanding convergence is achieved, then the rms error on the energy differences amounts to 0.002 eV. The 6-31 +g(d) basis is larger and yields a larger rms error: 0.006 eV. (C) 2007 Elsevier Ltd. All rights reserved.