cis-(+/-)-1-benzyl-3-ethyl-2-methoxycarbonylaziridine

• 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: cis-(+/-)-1-benzyl-3-ethyl-2-methoxycarbonylaziridine
• 英文别名: cis-1-benzyl-3-ethyl-2-methoxycarbonylaziridine；methyl (2S,3S)-1-benzyl-3-ethylaziridine-2-carboxylate
• 化学式: C₁₃H₁₇NO₂
• 分子量: 219.283
• InChiKey: HOXJESRVNGTRDQ-VHBIQUBJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  cis-(+/-)-1-benzyl-3-ethyl-2-methoxycarbonylaziridine 在 lithium aluminium tetrahydride 、 Amano PS Lipase 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.25h， 生成 cis-(2S,3S)-(+)-2-acetoxymethyl-1-benzyl-3-ethylaziridine
  参考文献：
  名称：

  A Novel Approach to a Precursor of the Carbapenem Antibiotic PS-5 via Aziridine Stereospecific Carbonylation

  摘要：

  Cobalt cartonyl-catalyzed carbonylative ring expansion of optically pure cis-1-benzyl-3-ethyl-2-hydroxymethylaziridine (5) to trans-beta -lactam (8) afforded a key precursor of the carbapenem antibiotic (+)-PS-5. Aziridine (5) was obtained in both enantiomerically pure forms by Amano PS lipase-catalyzed esterification in n-hexane using vinyl acetate as acyl donor. The stereochemical pathway of the carbonylation reaction was proved by configurational assignments through chemical correlation.

  DOI：

  10.3987/com-00-8974
• 作为产物：
  描述：

  反-2-戊酸甲酯 在 溴 作用下， 以 甲醇 、 四氯化碳 为溶剂， 生成 cis-(+/-)-1-benzyl-3-ethyl-2-methoxycarbonylaziridine
  参考文献：
  名称：

  关于环取代基在氮丙啶羰基化反应中的作用

  摘要：

  研究了环取代基对羰基钴催化羰基化官能化氮丙啶生成β-内酰胺的影响。已经合成了具有不同取代基和立体化学的多种氮丙啶，并将其进行羰基化。在不存在吸电子取代基的情况下，扩环成β-内酰胺，对于顺式-氮丙啶，总是获得较高的产率。此外，反应的区域选择性受环碳原子上取代基的性质影响。

  DOI：

  10.1016/s0040-4020(00)01152-2

文献信息

• Selectivity in the Addition Reactions of Organometallic Reagents to Aziridine-2-carboxaldehydes: The Effects of Protecting Groups and Substitution Patterns
  作者：Aman Kulshrestha、Jennifer M. Schomaker、Daniel Holmes、Richard J. Staples、James E. Jackson、Babak Borhan

  DOI：10.1002/chem.201101168

  日期：2011.10.24

  especially the electronic character and conformational preferences of the nitrogen protecting groups. To help rationalize the observed stereochemical outcomes, conformational and electronic structural analyses of a series of model systems representing the various substitution patterns have been explored by density functional calculations at the B3LYP/6‐31G* level of theory with the SM8 solvation model to account

  从优秀到卓越的立体选择性已发现在格氏和有机试剂和N的加成反应-保护的氮丙啶-2-羧醛。具体而言，苄基保护的顺式、叔丁氧羰基保护的反式获得了高顺式选择性和甲苯磺酰基保护的 2,3-二取代氮丙啶-2-甲醛。此外，还研究了环取代基、温度、溶剂和路易斯酸碱改性剂对速率和选择性的影响。添加的非对映异构偏好由底物氮丙啶的取代模式，尤其是氮保护基团的电子特征和构象偏好决定。为了帮助使观察到的立体化学结果合理化，已经通过 B3LYP/6-31G* 理论水平的密度泛函计算探索了一系列代表各种取代模式的模型系统的构象和电子结构分析，并使用 SM8 溶剂化模型来解释溶剂效应。
• On the effect of ring substituents in the carbonylation of aziridines
  作者：Paolo Davoli、Arrigo Forni、Irene Moretti、Fabio Prati、Giovanni Torre

  DOI：10.1016/s0040-4020(00)01152-2

  日期：2001.2

  The effect of ring substituents on the cobalt carbonyl-catalyzed carbonylation of functionalized aziridines to β-lactams has been investigated. A variety of aziridines with different substituents and stereochemistry has been synthesized and subjected to carbonylation. The ring expansion to β-lactam takes place in the absence of an electron-withdrawing substituent and higher yields are always obtained

  研究了环取代基对羰基钴催化羰基化官能化氮丙啶生成β-内酰胺的影响。已经合成了具有不同取代基和立体化学的多种氮丙啶，并将其进行羰基化。在不存在吸电子取代基的情况下，扩环成β-内酰胺，对于顺式-氮丙啶，总是获得较高的产率。此外，反应的区域选择性受环碳原子上取代基的性质影响。
• Reaction of vinyl triflates of α-keto esters with primary amines: efficient synthesis of aziridine carboxylates
  作者：Marie-José Tranchant、Vincent Dalla、Ivan Jabin、Bernard Decroix

  DOI：10.1016/s0040-4020(02)01031-1

  日期：2002.10

  Vinyl triflates of α-keto esters react smoothly with primary amines to provide aziridine carboxylates in good yields. In all cases, little or no stereoselectivity was observed. A mechanistic study has shown that aziridine carboxylates are strictly formed under kinetic control. The origin of this lack of stereoselectivity is explained by a non- or poorly stereoselective proton transfer.

  α-酮酯的乙烯基三氟甲磺酸酯与伯胺平稳反应，以高收率提供氮丙啶羧酸酯。在所有情况下，几乎没有或没有观察到立体选择性。机理研究表明，氮丙啶羧酸盐是在动力学控制下严格形成的。缺乏立体选择性的原因可以通过非选择性或较差的立体选择性质子转移来解释。
• A Novel Approach to a Precursor of the Carbapenem Antibiotic PS-5 via Aziridine Stereospecific Carbonylation
  作者：Paolo Davoli、Fabio Prati

  DOI：10.3987/com-00-8974

  日期：——

  Cobalt cartonyl-catalyzed carbonylative ring expansion of optically pure cis-1-benzyl-3-ethyl-2-hydroxymethylaziridine (5) to trans-beta -lactam (8) afforded a key precursor of the carbapenem antibiotic (+)-PS-5. Aziridine (5) was obtained in both enantiomerically pure forms by Amano PS lipase-catalyzed esterification in n-hexane using vinyl acetate as acyl donor. The stereochemical pathway of the carbonylation reaction was proved by configurational assignments through chemical correlation.