(±)-(trans)-ethyl 1-methyl-2-oxospiro[indoline-3,2'-oxirane]-3'-carboxylate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: (±)-(trans)-ethyl 1-methyl-2-oxospiro[indoline-3,2'-oxirane]-3'-carboxylate
• 英文别名: 2-carboethoxy-1′-methyl-2′-oxospiro[indoline-2,3′-oxirane]；ethyl 1-methyl-2-oxospiro[indoline-3,2'-oxirane]-3'-carboxylate；ethyl (2'S,3S)-1-methyl-2-oxospiro[indole-3,3'-oxirane]-2'-carboxylate
• 化学式: C₁₃H₁₃NO₄
• 分子量: 247.251
• InChiKey: NEUJFQYUPZIXDX-MFKMUULPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  59.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (±)-(trans)-ethyl 1-methyl-2-oxospiro[indoline-3,2'-oxirane]-3'-carboxylate 、 茚 在 2,4,6-triphenylpyrylium tetrafluoroborate 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 以81%的产率得到ethyl 1'-methyl-2'-oxo-2,3a,4,8b-tetrahydrospiro[indeno[1,2-b]furan-3,3'-indoline]-2-carboxylate
  参考文献：
  名称：

  PET催化螺[吲哚啉-3,2'-环氧乙烷] -2-酮与富电子烯烃的[3 + 2]反应合成螺[呋喃-3,3'-吲哚啉] -2'-酮

  摘要：

  合成了螺[呋喃-3,3'-吲哚啉] -2-酮和双螺[环烷烃-1,2'-呋喃-3'，3”-吲哚啉] -2”-酮的有效方法通过取代的螺[吲哚啉-3,2'-环氧乙烷] -2-酮与烯烃的光诱导电子转移催化的[3 + 2]反应，可以高收率和立体选择性。该反应通过螺开环[二氢吲哚-3,2'-环氧乙烷] -2-酮通过C β -O键裂解和随后的环加成与烯烃通过使用2,4,6-三苯基吡喃鎓tetarfluoroborate（TPT）作为敏化剂。

  DOI：

  10.1016/j.tet.2011.12.018
• 作为产物：
  描述：

  ethyl (E)-2-(1-methyl-2-oxoindolin-3-ylidene)acetate 在 奎宁 、 过氧化脲素 作用下， 以 二氯甲烷 为溶剂， 反应 16.17h， 以94%的产率得到(±)-(trans)-ethyl 1-methyl-2-oxospiro[indoline-3,2'-oxirane]-3'-carboxylate
  参考文献：
  名称：

  Quinine as an organocatalytic dual activator for the diastereoselective synthesis of spiro-epoxyoxindoles

  摘要：

  A highly efficient organocatalytic approach has been developed for the diastereoselective epoxidation of (E)-3-ylidene-indolin-2-one derivatives using readily available natural product quinine and urea-hydrogen peroxide (UHP) in DCM at 10 degrees C to afford trans spiro-epoxyoxindoles which were further utilized to obtain beta-hydroxy-alpha-amino esters by water mediated regioselective ring opening from the less hindered end with aniline derivatives, under sonication. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2013.10.115

文献信息

• Asymmetric Synthesis of Spirooxindoles via Nucleophilic Epoxidation Promoted by Bifunctional Organocatalysts
  作者：Martina Miceli、Andrea Mazziotta、Chiara Palumbo、Elia Roma、Eleonora Tosi、Giovanna Longhi、Sergio Abbate、Paolo Lupattelli、Giuseppe Mazzeo、Tecla Gasperi

  DOI：10.3390/molecules23020438

  日期：——

  catalysts displaying various effects that noticeably differ in terms of steric hindrance and electron demand; (ii) employed α-alkylidene oxindoles decorated with different substituents on the aromatic ring (11a–g), the exocylic double bond (11h–l), and the amide moiety (11m–v). The observed results suggest that the modification of the electron-withdrawing group (EWG) weakly conditions the overall outcomes

  考虑到我们实验室开发的缺电子烯烃有机催化环氧化反应的假设反应机理，我们研究了能够对安装在底物/催化剂/氧化剂内部的 H 键网络产生积极影响的关键因素。为了这个目标，我们已经： (i) 测试了一些催化剂，显示出在空间位阻和电子需求方面明显不同的各种效果；(ii) 使用在芳环 (11a-g)、环外双键 (11h-l) 和酰胺部分 (11m-v) 上装饰有不同取代基的 α-亚烷基羟吲哚。观察到的结果表明，吸电子基团 (EWG) 的修饰对整体结果的影响很小，相反，强烈的影响明确归因于 N 保护或 N 未保护的内酰胺框架。
• Organocatalytic stereoselective epoxidation of alpha‐alkylidene oxindoles using alpha,alpha‐diphenylprolinol in liposome membrane
  作者：Tecla Gasperi、Carola Tortora、Martina Miceli、Frank Steiniger、Peter Walde、Pasquale Stano

  DOI：10.1002/cctc.201801677

  日期：——

  We employed the membrane of 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phosphocholine (POPC) liposomes suspended in water as a microenvironment for carrying out the organocatalytic epoxidation of an α‐alkylidene oxindole. The reaction proceeds smoothly and displays diastereo‐ and enantio‐selectivity that differs from what is achieved under bulk solution conditions. The potential of organocatalytic approaches

  我们将悬浮在水中的1-棕榈酰基-2-油酰基-sn-甘油3-磷酸胆碱（POPC）脂质体膜用作微环境，以进行α-亚烷基ide吲哚的有机催化环氧化。反应平稳进行，显示出的非对映体和对映体选择性不同于在本体溶液条件下获得的非对映体和对映体选择性。简要讨论了在分散膜存在下有机催化方法在水相中进行合成转化的潜力。
• Noncovalent Organocatalysis: A Powerful Tool for the Nucleophilic Epoxidation of α-Ylideneoxindoles
  作者：Chiara Palumbo、Giuseppe Mazzeo、Andrea Mazziotta、Augusto Gambacorta、M. Antonietta Loreto、Antonella Migliorini、Stefano Superchi、Daniela Tofani、Tecla Gasperi

  DOI：10.1021/ol202646w

  日期：2011.12.2

  A novel asymmetric nucleophilic epoxidation for alpha-ylideneoxindole esters has been successfully devised, resulting in enantioenriched spiro compounds with two new contiguous stereocenters. The employed (S)-alpha,alpha-diphenylprolinol functions as a bifunctional catalyst, creating a complex H-bond network in conjunction with a substrate and an oxidant.