[(2R,3S)-3-(4-Methoxy-phenyl)-oxiranyl]-morpholin-4-yl-methanone | 727728-81-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: [(2R,3S)-3-(4-Methoxy-phenyl)-oxiranyl]-morpholin-4-yl-methanone
• 英文别名: [(2R,3S)-3-(4-methoxyphenyl)oxiran-2-yl]-morpholin-4-ylmethanone
• CAS: 727728-81-6
• 化学式: C₁₄H₁₇NO₄
• 分子量: 263.293
• InChiKey: IZHBCMWFKREBDQ-QWHCGFSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  51.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(2R,3S)-3-(4-Methoxy-phenyl)-oxiranyl]-morpholin-4-yl-methanone 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 1.0h， 生成 4-[(2R,3R)-3-azido-2-hydroxy-3-(4-methoxyphenyl)-1-oxo-propyl]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)-3-(4-methoxyphenyl)-1-morpholinoprop-2-en-1-one 在 叔丁基过氧化氢 三苯胂氧化物 、 S-1,1'-联-2-萘酚 、 samarium(III) isopropoxide 作用下， 以 四氢呋喃 、 癸烷 为溶剂， 反应 12.0h， 生成 [(2R,3S)-3-(4-Methoxy-phenyl)-oxiranyl]-morpholin-4-yl-methanone
  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+

文献信息

• 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.