O-benzyl tert-butyl glyoxylate oxime ether | 203127-16-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: O-benzyl tert-butyl glyoxylate oxime ether
• 英文别名: tert-butyl (2E)-2-phenylmethoxyiminoacetate
• CAS: 203127-16-6
• 化学式: C₁₃H₁₇NO₃
• 分子量: 235.283
• InChiKey: VXYQBTBXSNVOGZ-NTEUORMPSA-N

物化性质

• 沸点：
  316.5±35.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  O-benzyl tert-butyl glyoxylate oxime ether 在 正丁基锂 、 hexacarbonyl molybdenum 、 (R,r)-2,2-亚甲基双(4-苯基-2-噁唑啉) 作用下， 以 水 、 乙腈 为溶剂， 反应 1.25h， 生成 (S)-2-氨基-4-戊烯酸叔丁酯
  参考文献：
  名称：

  Enantioselective allylation of α-ketoester oximes with an external chiral ligand: Asymmetric synthesis of allylglycines and allylalanine

  摘要：

  A highly enantioselective allylation of oximes of alpha-ketoesters is described with phenyl substituted chiral bis(oxazoline) as external ligand of allylzinc reagents. This method provides an efficient and convenient access to N-benzyloxy allylglycine, allylglycine and chain substituted variants with high enantiomeric purities. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/s0040-4039(96)02112-0
• 作为产物：
  描述：

  di-tert-butyl fumarate 在 二甲基硫 、 氧气 、 臭氧 作用下， 以 吡啶 、 二氯甲烷 为溶剂， 反应 7.0h， 生成 O-benzyl tert-butyl glyoxylate oxime ether
  参考文献：
  名称：

  Thermal Hetero [3 + 2] Cycloaddition of Dipolar Trimethylenemethane to O-Alkyloximes. Straightforward Synthetic Routes to Substituted Pyrrolidines and Prolines

  摘要：

  Thermal hetero [3 + 2] cycloaddition reaction of a dipolar trimethylenemethane 2 with an O-alkyloxime produces a substituted pyrrolidine. Thus, heating of a mixture of an alkylidenecyclopropane 1 an anti-O-alkyloxime 3 proceeds smoothly in good yield to give a substituted pyrrolidine 4 bearing a ketene acetal group in its 3-position, which upon hydrolysis under mild conditions gives a 3-alkoxycarbonylpyrrolidne 5 in quantitative yield. On the other hand, the cycloaddition to a syn-oxime is extremely slow. The cycloaddition reaction can be achieved by starting with nearly equimolar quantities of the two starting materials, and the reaction is quite insensitive to the choice of solvent and to the presence of oxygen and water. In the reaction of a substituted methylenecyclopropane 1 (R not equal H), the reaction may take place with high regio-and stereoselectivity, which is in consonance with the concerted nature of the cycloaddition reaction. The present synthesis represents one of the rare examples of the imine-based route to pyrrolidines, which have been much less explored than the 1,3-dipolar cycloaddition route using olefin and azomethine ylide.

  DOI：

  10.1021/jo972302y

文献信息

• Indium mediated allylation of glyoxylate oxime ethers, esters and cyanoformates
  作者：Dougal J. Ritson、Russell J. Cox、John Berge

  DOI：10.1039/b402764g

  日期：——

  An indium mediated procedure has been developed for the allylation of activated O-functionalised oximes and nitriles as exemplified by a variety of glyoxylate derivatives. This method gives the corresponding free (or protected) amine in a one pot-process. The method is regiospecific and is carried out under remarkably mild conditions so that even oxime esters can be subjected to the typical reaction conditions.

  已开发出一种铟介导的方法，用于活化的O-官能化肟和腈的烯丙基化，如多种甘油酸衍生物的实例所示。该方法可在一步反应中获得相应的自由（或保护）胺。该方法具有区域选择性，并在非常温和的条件下进行，因此即使是肟酯也可以承受典型的反应条件。
• Synthesis of 2‐Azanorbornanes via Strain‐Release Formal Cycloadditions Initiated by Energy Transfer
  作者：Yu‐Che Chang、Christophe Salome、Thomas Fessard、M. Kevin Brown

  DOI：10.1002/anie.202314700

  日期：2023.12.18

  Rigid bicycles are becoming more popular in the pharmaceutical industry because they allow for expansion to new and unique chemical spaces. This work describes a new strategy to construct 2‐azanorbornanes, which can act as rigid piperidine/pyrrolidine scaffolds with well‐defined exit vectors. To achieve the synthesis of 2‐azanorbornanes, new strain‐release reagent, azahousane, is introduced along with its photosensitized strain‐release formal cycloaddition with alkenes. Furthermore, new reactivity between a housane and an imine is disclosed. Both strategies lead to various substituted 2‐azanorbornanes with good selectivities.

  摘要刚性自行车在制药行业越来越受欢迎，因为它们可以扩展到新的独特的化学空间。这项工作描述了一种构建 2-azanorbornanes 的新策略，它可以作为具有明确出口载体的刚性哌啶/吡咯烷支架。为了合成 2-氮杂降冰片烷，引入了新的应变释放试剂氮杂环烷及其与烯烃的光敏应变释放正式环化反应。此外，研究还揭示了一种新的反应性。这两种策略都能产生具有良好选择性的各种取代的 2-氮杂降冰片烷。
• Thermal Hetero [3 + 2] Cycloaddition of Dipolar Trimethylenemethane to <i>O</i>-Alkyloximes. Straightforward Synthetic Routes to Substituted Pyrrolidines and Prolines
  作者：Shigeru Yamago、Masaharu Nakamura、Xiao Qun Wang、Masao Yanagawa、Shuzo Tokumitsu、Eiichi Nakamura

  DOI：10.1021/jo972302y

  日期：1998.3.1

  Thermal hetero [3 + 2] cycloaddition reaction of a dipolar trimethylenemethane 2 with an O-alkyloxime produces a substituted pyrrolidine. Thus, heating of a mixture of an alkylidenecyclopropane 1 an anti-O-alkyloxime 3 proceeds smoothly in good yield to give a substituted pyrrolidine 4 bearing a ketene acetal group in its 3-position, which upon hydrolysis under mild conditions gives a 3-alkoxycarbonylpyrrolidne 5 in quantitative yield. On the other hand, the cycloaddition to a syn-oxime is extremely slow. The cycloaddition reaction can be achieved by starting with nearly equimolar quantities of the two starting materials, and the reaction is quite insensitive to the choice of solvent and to the presence of oxygen and water. In the reaction of a substituted methylenecyclopropane 1 (R not equal H), the reaction may take place with high regio-and stereoselectivity, which is in consonance with the concerted nature of the cycloaddition reaction. The present synthesis represents one of the rare examples of the imine-based route to pyrrolidines, which have been much less explored than the 1,3-dipolar cycloaddition route using olefin and azomethine ylide.
• Enantioselective allylation of α-ketoester oximes with an external chiral ligand: Asymmetric synthesis of allylglycines and allylalanine
  作者：Stephen Hanessian、Rui-Yang Yang

  DOI：10.1016/s0040-4039(96)02112-0

  日期：1996.12

  A highly enantioselective allylation of oximes of alpha-ketoesters is described with phenyl substituted chiral bis(oxazoline) as external ligand of allylzinc reagents. This method provides an efficient and convenient access to N-benzyloxy allylglycine, allylglycine and chain substituted variants with high enantiomeric purities. Copyright (C) 1996 Elsevier Science Ltd