ethyl 1-benzyl-2-oxoindoline-3-carboxylate | 156115-78-5

• 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: ethyl 1-benzyl-2-oxoindoline-3-carboxylate
• 英文别名: Ethyl 1-benzyl-2-oxoindole-3-carboxylate；ethyl 1-benzyl-2-oxo-3H-indole-3-carboxylate
• CAS: 156115-78-5
• 化学式: C₁₈H₁₇NO₃
• 分子量: 295.338
• InChiKey: HDYDJJUWZGRTQH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 1-benzyl-2-oxoindoline-3-carboxylate 在 [Ir(dF(CF₃)ppy)₂(dtbbpy)](PF₆) 、 碳酸氢钠 作用下， 以 2,2,2-三氟乙醇 为溶剂， 生成 ethyl 1-benzyl-3-hydroxy-2-oxoindoline-3-carboxylate
  参考文献：
  名称：

  光串联催化：通过可见光诱导的重氮酰胺通过有氧氧化序列的环化反应，有效合成3-酯-3-羟基-2-氧吲哚

  摘要：

  已经成功开发了基于单一铱光催化剂的前所未有的光串联催化。这种强大的策略包括两个机械上截然不同的催化循环，即光催化能量转移（ET）和单电子转移（SET）。新颖的方案允许在非常温和的条件下，通过环化/有氧氧化序列，从容易获得的重氮酰胺快速高效地构建生物学上和合成上重要的3-酯-3-羟基-2-吲哚衍生物。

  DOI：

  10.1002/asia.201402990
• 作为产物：
  描述：

  N-Benzyl-2-diazo-N-phenylmalonamic acid ethyl ester 在 [Ir(dF(CF₃)ppy)₂(dtbbpy)](PF₆) 作用下， 以 2,2,2-三氟乙醇 为溶剂， 生成 ethyl 1-benzyl-2-oxoindoline-3-carboxylate
  参考文献：
  名称：

  光串联催化：通过可见光诱导的重氮酰胺通过有氧氧化序列的环化反应，有效合成3-酯-3-羟基-2-氧吲哚

  摘要：

  已经成功开发了基于单一铱光催化剂的前所未有的光串联催化。这种强大的策略包括两个机械上截然不同的催化循环，即光催化能量转移（ET）和单电子转移（SET）。新颖的方案允许在非常温和的条件下，通过环化/有氧氧化序列，从容易获得的重氮酰胺快速高效地构建生物学上和合成上重要的3-酯-3-羟基-2-吲哚衍生物。

  DOI：

  10.1002/asia.201402990

文献信息

• Highly Enantioselective Michael Addition of 2-Oxindole- 3-carboxylate Esters to Nitroolefins Promoted by Cinchona Alkaloid-Thiourea-Brønsted Acid Cocatalysts
  作者：Xianjie Chen、Wei Zhu、Wangke Qian、Enguang Feng、Yu Zhou、Jinfang Wang、Hualiang Jiang、Zhu-Jun Yao、Hong Liu

  DOI：10.1002/adsc.201200206

  日期：2012.8.13

  A highly efficient organocatalyzed Michael addition of 2-oxindole-3-carboxylate esters to nitroolefins using a Cinchona alkaloid-thiourea and an achiral Brønsted acid as cooperative organocatalysts is reproted that affords significantly improved enantioselectivity and diastereoselectivity. It also provides an efficient approach to the synthesis of spirooxindole derivatives with high enantioselectivity

  使用金鸡纳生物碱-硫脲和非手性布朗斯台德酸作为协同有机催化剂，可以高效地将2-氧吲哚-3-羧酸酯的迈克尔加成到硝基烯烃上，从而大大提高了对映选择性和非对映选择性。它还为合成具有高对映选择性的螺并恶吲哚衍生物提供了一种有效的方法。
• Visible-Light-Driven Photocatalytic Activation of Inert Sulfur Ylides for 3-Acyl Oxindole Synthesis
  作者：Xu-Dong Xia、Liang-Qiu Lu、Wen-Qiang Liu、Dong-Zhen Chen、Yu-Han Zheng、Li-Zhu Wu、Wen-Jing Xiao

  DOI：10.1002/chem.201600871

  日期：2016.6.13

  Bicarbonyl‐substituted sulfur ylide is a useful, but inert reagent in organic synthesis. Usually, harsh reaction conditions are required for its transformation. For the first time, it was demonstrated that a new, visible‐light photoredox catalytic annulation of sulfur ylides under extremely mild conditions, permits the synthesis of oxindole derivatives in high selectivities and efficiencies. The key

  联羰基取代的硫代叶立德是有机合成中有用但惰性的试剂。通常，其转化需要苛刻的反应条件。首次证明，在极其温和的条件下，新型的可见光光氧化还原催化的硫化物锡环氧化物可以高选择性和高效率地合成羟吲哚衍生物。其成功的关键是惰性酰胺和酰基稳定的硫磺化物的光催化单电子转移（SET）氧化成反应性自由基阳离子，这很容易随着分子内CH功能化而产生最终产物。
• Electrochemical Synthesis of Dimeric 2-Oxindole Sharing Vicinal Quaternary Centers Employing Proton-Coupled Electron Transfer
  作者：Sulekha Sharma、Avishek Roy、Kundan Shaw、Alakesh Bisai、Amit Paul

  DOI：10.1021/acs.joc.0c01621

  日期：2020.12.4

  building blocks for the total synthesis of pyrroloindoline alkaloids. Furthermore, this work demonstrates in-depth mechanistic insights employing electrochemistry, which suggests a stepwise one proton transfer (PT) and two electron transfer (ET) processes. Most significantly, reaction rate acceleration has been demonstrated by exploiting the base-assisted proton-coupled electron transfer (PCET) pathway. Hence

  已经在温和的电化学条件下开发了3-取代的2-氧吲哚的二聚反应，避免了有毒的化学氧化剂和金属副产物。这种方法形成了C（sp 3）–C（sp 3）在具有广泛的底物范围的2-氧吲哚的两个配偶体的假苄基位置键合。这些二聚体结构基序是吡咯并吲哚啉生物碱总合成的重要组成部分。此外，这项工作展示了利用电化学的深入机械学见解，这表明了逐步的一个质子转移（PT）和两个电子转移（ET）过程。最重要的是，通过利用碱辅助的质子耦合电子转移（PCET）途径已证明了反应速率的加快。因此，这项工作借助自然界最喜欢的动力学途径（即PCET），在有机合成领域开辟了新的领域，以降低动力学障碍。
• Two-Electron- and One-Electron-Transfer Pathways for TEMPO-Catalyzed Greener Electrochemical Dimerization of 3-Substituted-2-Oxindoles
  作者：Sulekha Sharma、Saina Shaheeda、Kundan Shaw、Alakesh Bisai、Amit Paul

  DOI：10.1021/acscatal.2c06361

  日期：2023.2.3

  method for synthesis optimization instead of lengthy product isolation, (b) prevention of electrode passivation employing electrocatalysis routes, (c) recovery of the electrolyte, and (d) mild reaction conditions employing control potential electrolysis. Finally, an efficient electrochemical oxidation strategy has been demonstrated for the total synthesis of a dimeric hexahydropyrrolo[2,3-b]indole alkaloids

  二聚 3-取代的 2-oxindoles 是生物碱全合成的基本组成部分。在此，三种不同类型的 3-substituted-2-oxindoles 被二聚化，共有 41 个实例使用 TEMPO 作为氧化还原介体和 TEMPO +作为原位生成的电催化剂，使用控制电势电解在仅 0.8 V 的施加电势下与银/银+非水参比电极。在没有 TEMPO 的情况下，这些反应不会产生任何产物形成，保持其他实验条件相同。双电子和单电子转移途径的运作取决于 2-oxindoles 的氧化电位。具有较低氧化能垒的双电子转移途径的 3-Carboxylate-2-oxindoles 遵循氢化物转移机制产生碳阳离子，此后与烯醇形式的羟吲哚反应产生二聚 2-oxindoles。另一方面，与 3-carboxylate-2-oxindoles 相比，3-alkyl-2-oxindoles 和 3-alkylcarboxylate-2-oxindoles
• Ligand Effects in the Rhodium(II)-Catalyzed Reactions of .alpha.-Diazoamides. Oxindole Formation is Promoted by the Use of Rhodium(II) Perfluorocarboxamide Catalysts
  作者：David S. Brown、Mark C. Elliott、Christopher J. Moody、Timothy J. Mowlem、Joseph P. Jr. Marino、Albert Padwa

  DOI：10.1021/jo00088a028

  日期：1994.5

  An improved procedure for the preparation of ethyl 2-diazomalonyl chloride ws developed which involves the reaction of ethyl diazoacetate with triphosgene. Using this diazo acid chloride, it was possible to prepare a variety of diazoamides from substituted amines. The rhodium(II)-catalyzed decomposition of these diazoamides was studied in order to probe the chemoselectivity of the carbenoid intermediates in intramolecular insertion reactions. Rhodium(II) acetate decomposition of N-benzyl-2-diazo-N-phenylmalonamic acid ethyl ester resulted in intramolecular C-H insertion to give ethyl 1,4-diphenyl-2-oxoazetidine-3-carboxylate. By changing the catalyst ligand to trifluoroacetamide, beta-lactam formation was completely suppressed in favor of the aromatic C-H insertion which produces an oxindole as the only detectable product. The competition between aliphatic and aromatic carbon-hydrogen insertion of 2-diazo-N-phenylmalonamic acid ethyl ester provides another example of ligand effectiveness in controlling chemoselectivity in dirhodium(II)-catalyzed metal carbene reactions. Thus, treatment of the N-isobutyldiazoanilide with rhodium(II) acetate results in exclusive aliphatic C-H insertion giving 4,4-dimethyl-2-oxo-1-phenylpyrrolidine-3-carboxylic acid ethyl ester, while the perfluorobutyramide ligand promotes oxidinole formation by aromatic C-H insertion. Several other rhodium(II)-catalyzed reactions were studied and were found to be highly catalyst dependent, rhodium(II) perfluorocarboxamides promoting aromatic C-H insertion, and hence oxindole formation, over O-H insertion, cyclization onto adjacent triple bonds, or cyclization to generate 1,3-dipolar intermediates.