methyl (2S,αR)-N-α-methylbenzylazetidine-2-carboxylate | 249734-39-2

• 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: methyl (2S,αR)-N-α-methylbenzylazetidine-2-carboxylate
• 英文别名: methyl (2S,1R')-1-phenylethylazetidine-2-carboxylate；methyl (2S)-1-[(1R)-1-phenylethyl]azetidine-2-carboxylate
• CAS: 249734-39-2
• 化学式: C₁₃H₁₇NO₂
• 分子量: 219.283
• InChiKey: FMYIXIBSKQXTLX-PWSUYJOCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (2S,αR)-N-α-methylbenzylazetidine-2-carboxylate 在 盐酸 、 palladium dihydroxide 、 氢气 作用下， 以95%的产率得到(S)-(-)-2-羧基环丁胺
  参考文献：
  名称：

  Preparation of enantiopure 2-acylazetidines and their reactions with chloroformates

  摘要：

  Enantiopure 1-phenylethylazetidine-2-carboxylates and 2-acylazetidines were prepared and reacted with chloroformates to yield alpha-chloro-gamma-amino butyric acid esters and ketones from ring opening reaction of azetidinium ion intermediate in a completely regio- and stereoselective manner. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.11.033
• 作为产物：
  描述：

  2,4-二溴丁酸甲酯 、 R(+)-alpha-甲基苄胺 在 potassium carbonate 作用下， 以 水 、 乙腈 为溶剂， 反应 6.5h， 以32%的产率得到methyl (2R,αR)-N-α-methylbenzylazetidine-2-carboxylate
  参考文献：
  名称：

  串联的分子内氮杂环丁烷开环/闭合级联反应合成螺环丙基γ-内酰胺：合成和机理方面

  摘要：

  报道了新颖的分子内氮杂环丁烷开环/闭合级联反应的范围和局限性，其从氮杂环丁烷以高区域和立体选择性提供螺环丙基γ-内酰胺。该方法的关键步骤是通过用TMSOTf和TEA处理产生的甲硅烷基烯酮缩醛使TMSOTf活化的氮杂环丁烷环S N 2型开环。这项研究是氮杂环丁烷亲核开环的非常罕见的例子，它不需要通过N-烷基化或使用N形成季铵盐-吸电子基团。该方法在2-氮杂环丁酮系统中的应用导致反应活性的完全改变，并通过空前的涉及酯受体和亚氨酸甲硅烷基酯的Mukaiyama aldol-like反应提供6-氮杂双环[3.2.0]庚烷衍生物。

  DOI：

  10.1016/j.tet.2012.03.111

文献信息

• Enantioselective addition of alkynylzinc to arylaldehydes catalyzed by azetidino amino alcohols bearing an additional stereogenic center
  作者：Jun-Long Niu、Min-Can Wang、Liu-jie Lu、Guo-Liang Ding、Hui-Jie Lu、Qing-Tao Chen、Mao-Ping Song

  DOI：10.1016/j.tetasy.2009.10.031

  日期：2009.11

  Chiral azetidino amino alcohol ligands bearing an additional stereogenic center were readily prepared and used as catalysts for the asymmetric addition of alkynylzinc to aromatic aldehydes with enantioselectivities of up to 87% ee. The relationship between the reaction enantioselectivity and the structure of the chiral ligands was also evaluated in this reaction. The experimental results showed that the enantioselectivity level of the reaction was greatly influenced by the second stereogenic center attached to azetidine ring, but the stereochemical sense was only determined by the configuration of the azetidine ring. A possible transition structure for the catalytic asymmetric addition was also proposed. (C) 2009 Elsevier Ltd. All rights reserved.
• Preparation of enantiopure 2-acylazetidines and their reactions with chloroformates
  作者：Sang-ho Ma、Doo Ha Yoon、Hyun-Joon Ha、Won Koo Lee

  DOI：10.1016/j.tetlet.2006.11.033

  日期：2007.1

  Enantiopure 1-phenylethylazetidine-2-carboxylates and 2-acylazetidines were prepared and reacted with chloroformates to yield alpha-chloro-gamma-amino butyric acid esters and ketones from ring opening reaction of azetidinium ion intermediate in a completely regio- and stereoselective manner. (c) 2006 Elsevier Ltd. All rights reserved.
• Synthesis of spirocyclopropyl γ-lactams by tandem intramolecular azetidine ring-opening/closing cascade reaction: synthetic and mechanistic aspects
  作者：Pierre-Antoine Nocquet、Damien Hazelard、Philippe Compain

  DOI：10.1016/j.tet.2012.03.111

  日期：2012.6

  intramolecular azetidine ring-opening/closing cascade reaction affording spirocyclopropyl γ-lactams from azetidines in high regio- and stereoselectivity is reported. The key step of the process is a SN2-type ring-opening of TMSOTf-activated azetidine rings by silyl ketene acetals generated by treatment with TMSOTf and TEA. This study is a very rare example of nucleophilic ring-opening of azetidines that

  报道了新颖的分子内氮杂环丁烷开环/闭合级联反应的范围和局限性，其从氮杂环丁烷以高区域和立体选择性提供螺环丙基γ-内酰胺。该方法的关键步骤是通过用TMSOTf和TEA处理产生的甲硅烷基烯酮缩醛使TMSOTf活化的氮杂环丁烷环S N 2型开环。这项研究是氮杂环丁烷亲核开环的非常罕见的例子，它不需要通过N-烷基化或使用N形成季铵盐-吸电子基团。该方法在2-氮杂环丁酮系统中的应用导致反应活性的完全改变，并通过空前的涉及酯受体和亚氨酸甲硅烷基酯的Mukaiyama aldol-like反应提供6-氮杂双环[3.2.0]庚烷衍生物。