1-benzyl-2-tert-butoxycarbonyl-3-phenylaziridine

• 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: 1-benzyl-2-tert-butoxycarbonyl-3-phenylaziridine
• 英文别名: (-)-tert-butyl (2S,3R)-1-benzyl-3-phenylaziridine-2-carboxylate；tert-butyl (2S,3R)-1-benzyl-3-phenylaziridine-2-carboxylate
• 化学式: C₂₀H₂₃NO₂
• 分子量: 309.408
• InChiKey: BYAHCNVSHDCSRN-IZKAZRHKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  29.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-benzyl-2-tert-butoxycarbonyl-3-phenylaziridine 在 10% Pd/C 、 氢气 作用下， 以 甲醇 为溶剂， 50.0 ℃ 、101.33 kPa 条件下， 反应 24.0h， 以75%的产率得到L-苯基丙氨酸叔丁酯
  参考文献：
  名称：

  General Entry to Asymmetric One-Pot [N + 2 + n] Cyclization for the Synthesis of Three- to Seven-Membered Azacycloalkanes

  摘要：

  Enantio- and diastereoselective one-pot synthesis of three- to seven-membered cis-azaheterocycles was achieved using a triggered asymmetric conjugate addition reaction of lithium amide with an enoate, followed by alkylation of the resulting lithium enolate with alpha,omega-dihaloalkane and N-alkylation. Isomerization of cis-azaheterocycles with a base yielded the trans-product, constituting a one-pot synthesis of cis-azacycles and a two-step synthesis of trans-azacycles. The four-step asymmetric synthesis of nemonapride highlights the general utility of the method.

  DOI：

  10.1021/jo301495a
• 作为产物：
  描述：

  1-氯-2-碘乙烷 、 tert-butyl cinnamate 、 在 (1S,2S)-1,2-dimethoxy-1,2-diphenylethane 作用下， 以 甲苯 为溶剂， 反应 2.21h， 以94%的产率得到1-benzyl-2-tert-butoxycarbonyl-3-phenylaziridine
  参考文献：
  名称：

  General Entry to Asymmetric One-Pot [N + 2 + n] Cyclization for the Synthesis of Three- to Seven-Membered Azacycloalkanes

  摘要：

  Enantio- and diastereoselective one-pot synthesis of three- to seven-membered cis-azaheterocycles was achieved using a triggered asymmetric conjugate addition reaction of lithium amide with an enoate, followed by alkylation of the resulting lithium enolate with alpha,omega-dihaloalkane and N-alkylation. Isomerization of cis-azaheterocycles with a base yielded the trans-product, constituting a one-pot synthesis of cis-azacycles and a two-step synthesis of trans-azacycles. The four-step asymmetric synthesis of nemonapride highlights the general utility of the method.

  DOI：

  10.1021/jo301495a

文献信息

• Mechanistic approaches to asymmetric synthesis of aziridines from guanidinium ylides and aryl aldehydes
  作者：Toyokazu Haga、Tsutomu Ishikawa

  DOI：10.1016/j.tet.2005.01.088

  日期：2005.3

  synthesis from guanidinium ylides and aryl aldehydes, reactions were systematically carried out by using a variety of p-substituted benzaldehydes under modified conditions. Two kinds of reaction mechanisms controlled by the nature of the p-substituents of aryl aldehydes is proposed for the two-steps aziridine synthesis composed of a C–C bond formation by nucleophilic addition of guanidinium ylides to aryl

  为了接近更实际的机制，由胍基碘化物和芳基醛合成不对称氮丙啶，在改性条件下，通过使用各种对位取代的苯甲醛系统地进行了反应。提出了由芳基醛的对位取代基的性质控制的两种反应机理，用于两步氮丙啶合成，该过程由亲核加成啶基团到芳基醛（步骤1）的CC键形成分子内亲核取代法制备氮丙啶产物的中间体加合物（步骤2）。AS N在使用EDG取代的苯甲醛进行不对称合成的步骤2中，提出了通过阳离子样过渡态形成i样的机理，而在使用EWG取代的苯甲醛的情况下，提出了一种S N 2样机理。基于氮丙啶产物中非对映异构体比率的Hammett分析与这两种机制中提议的速率测定步骤一致。第二个Hammett分析基于氮丙啶产物的对映体比率，清楚地揭示了步骤1和步骤2之间对电子取代基效应的磁化率差异。
• Guanidinium Ylides as a New and Recyclable Source for Aziridines and Their Roles as Chiral Auxiliaries
  作者：Kihito Hada、Toshiko Watanabe、Toshio Isobe、Tsutomu Ishikawa

  DOI：10.1021/ja0107024

  日期：2001.8.1
• General Entry to Asymmetric One-Pot [<i>N</i> + 2 + <i>n</i>] Cyclization for the Synthesis of Three- to Seven-Membered Azacycloalkanes
  作者：Shingo Harada、Takeo Sakai、Kiyosei Takasu、Ken-ichi Yamada、Yasutomo Yamamoto、Kiyoshi Tomioka

  DOI：10.1021/jo301495a

  日期：2012.9.7

  Enantio- and diastereoselective one-pot synthesis of three- to seven-membered cis-azaheterocycles was achieved using a triggered asymmetric conjugate addition reaction of lithium amide with an enoate, followed by alkylation of the resulting lithium enolate with alpha,omega-dihaloalkane and N-alkylation. Isomerization of cis-azaheterocycles with a base yielded the trans-product, constituting a one-pot synthesis of cis-azacycles and a two-step synthesis of trans-azacycles. The four-step asymmetric synthesis of nemonapride highlights the general utility of the method.