4-[(2R,3S)-2,3-epoxy-1-oxo-5-phenylpentenyl]morpholine | 677729-70-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: 4-[(2R,3S)-2,3-epoxy-1-oxo-5-phenylpentenyl]morpholine
• 英文别名: morpholin-4-yl-[(2R,3S)-3-(2-phenylethyl)oxiran-2-yl]methanone
• CAS: 677729-70-3
• 化学式: C₁₅H₁₉NO₃
• 分子量: 261.321
• InChiKey: QRPSLGBSCKCRFC-UONOGXRCSA-N

物化性质

• 熔点：
  66 °C(Solv: ethyl ether (60-29-7))
• 沸点：
  446.3±45.0 °C(Predicted)
• 密度：
  1.196±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  42.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-[(2R,3S)-2,3-epoxy-1-oxo-5-phenylpentenyl]morpholine 在 叠氮基三甲基硅烷 、 三苯胂氧化物 、 samarium(III) isopropoxide 、 盐酸 作用下， 以 四氢呋喃 、 癸烷 、 甲醇 为溶剂， 反应 12.0h， 生成 4-[(2R,3R)-3-azido-2-hydroxy-1-oxo-5-phenyl]morpholine
  参考文献：
  名称：

  Dynamic Ligand Exchange of the Lanthanide Complex Leading to Structural and Functional Transformation:  One-Pot Sequential Catalytic Asymmetric Epoxidation-Regioselective Epoxide-Opening Process

  摘要：

  The characteristic property of the lanthanide complex, which easily undergoes a dynamic ligand exchange and alters its structure and function in situ, is described. After the completion of the catalytic asymmetric epoxidation of various a,beta-unsaturated amides 2 in the presence of the Sm-(S)-BINOL-Ph3As=O (1:1:1) complex 1 (2-10 mol %), the addition of Me3SiN3 directly to the reaction mixture led to smooth epoxide-opening at room temperature, affording the corresponding anti-beta-azido-alpha-hydroxyamide 4 in excellent overall yield (up to 99%) with complete regioselectivity and excellent enantiomeric excess (up to >99%). The key to the success of the sequential process was the in situ generation of the highly reactive samarium azide complex through dynamic ligand exchange. In situ IR spectroscopy and other experiments provided strong evidence that the samariurn azide complex was generated. In addition, the relatively high Lewis basicity of the amide moiety had a key role in the high reactivity of both the epoxidation and the epoxide-opening reactions. Examinations of other nucleophiles such as sulfur or carbon nucleophiles as well as transformations of epoxide-opened products are also described.

  DOI：

  10.1021/ja043770+
• 作为产物：
  描述：

  (E)-1-morpholin-4-yl-5-phenyl-pent-2-en-1-one 在 叔丁基过氧化氢 、 S-1,1'-联-2-萘酚 三苯胂 、 4 A molecular sieve 、 samarium(III) isopropoxide 作用下， 以 四氢呋喃 、 癸烷 为溶剂， 反应 8.0h， 以100%的产率得到4-[(2R,3S)-2,3-epoxy-1-oxo-5-phenylpentenyl]morpholine
  参考文献：
  名称：

  基于α，β-不饱和吗啉基酰胺的高度催化剂控制的环氧化，对1,3-多元醇阵列的所有可能的立体异构体进行对映和非对映选择性合成的策略：在天然产物合成中的应用。

  摘要：

  我们描述了1,3-多元醇阵列的所有可能的立体异构体的对映体和非对映体选择性合成的新策略。此策略依赖于由Sm-BINOL-Ph（3）As [双键] O（1：1：1）配合物促进的α，β-不饱和吗啉基酰胺的高度催化剂控制的环氧化，然后是吗啉基的转化酰胺成酮和非对映选择性酮还原。使用5-10 mol％的Sm络合物可实现高度对映体（高达> 99％ee）或非对映选择性（高达> 99.5：0.5）的环氧化反应，从而提供合成上非常有用的，光学上几乎纯净的α，β-环氧吗啉基酰胺。 。环氧化的立体选择性是由BINOL的手性控制的，对底物的固有的非对映界面优先性是压倒性的。与高选择性催化的环氧化反应的合成和抗选择性酮还原反应相结合，为合成1,3-多元醇阵列的所有可能的立体异构体提供了一种迭代策略。合成了1,3,5,7-四醇阵列的八种可能的立体异构体，具有很高的立体选择性。此外，通过几种1,3-多元醇/α-吡喃酮

  DOI：

  10.1002/chem.200305709

文献信息

• Strategy for Enantio- and Diastereoselective Syntheses of All Possible Stereoisomers of 1,3-Polyol Arrays Based on a Highly Catalyst-Controlled Epoxidation ofα,β-Unsaturated Morpholinyl Amides: Application to Natural Product Synthesis
  作者：Shin-ya Tosaki、Yoshihiro Horiuchi、Tetsuhiro Nemoto、Takashi Ohshima、Masakatsu Shibasaki

  DOI：10.1002/chem.200305709

  日期：2004.3.19

  strategy for enantio- and diastereoselective syntheses of all possible stereoisomers of 1,3-polyol arrays. This strategy relies on a highly catalyst-controlled epoxidation of alpha,beta-unsaturated morpholinyl amides promoted by the Sm-BINOL-Ph(3)As[double bond]O (1:1:1) complex, followed by a conversion of morpholinyl amides into ketones and diastereoselective ketone reduction. Highly enantio- (up to >99

  我们描述了1,3-多元醇阵列的所有可能的立体异构体的对映体和非对映体选择性合成的新策略。此策略依赖于由Sm-BINOL-Ph（3）As [双键] O（1：1：1）配合物促进的α，β-不饱和吗啉基酰胺的高度催化剂控制的环氧化，然后是吗啉基的转化酰胺成酮和非对映选择性酮还原。使用5-10 mol％的Sm络合物可实现高度对映体（高达> 99％ee）或非对映选择性（高达> 99.5：0.5）的环氧化反应，从而提供合成上非常有用的，光学上几乎纯净的α，β-环氧吗啉基酰胺。 。环氧化的立体选择性是由BINOL的手性控制的，对底物的固有的非对映界面优先性是压倒性的。与高选择性催化的环氧化反应的合成和抗选择性酮还原反应相结合，为合成1,3-多元醇阵列的所有可能的立体异构体提供了一种迭代策略。合成了1,3,5,7-四醇阵列的八种可能的立体异构体，具有很高的立体选择性。此外，通过几种1,3-多元醇/α-吡喃酮
• Dynamic Ligand Exchange of the Lanthanide Complex Leading to Structural and Functional Transformation:  One-Pot Sequential Catalytic Asymmetric Epoxidation-Regioselective Epoxide-Opening Process
  作者：Shin-ya Tosaki、Riichiro Tsuji、Takashi Ohshima、Masakatsu Shibasaki

  DOI：10.1021/ja043770+

  日期：2005.2.1

  The characteristic property of the lanthanide complex, which easily undergoes a dynamic ligand exchange and alters its structure and function in situ, is described. After the completion of the catalytic asymmetric epoxidation of various a,beta-unsaturated amides 2 in the presence of the Sm-(S)-BINOL-Ph3As=O (1:1:1) complex 1 (2-10 mol %), the addition of Me3SiN3 directly to the reaction mixture led to smooth epoxide-opening at room temperature, affording the corresponding anti-beta-azido-alpha-hydroxyamide 4 in excellent overall yield (up to 99%) with complete regioselectivity and excellent enantiomeric excess (up to >99%). The key to the success of the sequential process was the in situ generation of the highly reactive samarium azide complex through dynamic ligand exchange. In situ IR spectroscopy and other experiments provided strong evidence that the samariurn azide complex was generated. In addition, the relatively high Lewis basicity of the amide moiety had a key role in the high reactivity of both the epoxidation and the epoxide-opening reactions. Examinations of other nucleophiles such as sulfur or carbon nucleophiles as well as transformations of epoxide-opened products are also described.