1-Allyl-2-oxo-2,3-dihydro-1H-indole-3-carboxylic acid ethyl ester

• 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: 1-Allyl-2-oxo-2,3-dihydro-1H-indole-3-carboxylic acid ethyl ester
• 英文别名: ethyl 2-oxo-1-prop-2-enyl-3H-indole-3-carboxylate
• 化学式: C₁₄H₁₅NO₃
• 分子量: 245.278
• InChiKey: KLIPLWFMTILHRC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  1-Allyl-2-oxo-2,3-dihydro-1H-indole-3-carboxylic acid ethyl ester 在 (4,4'-di-tert-butyl-2,2'-dipyridyl)-bis-(2-phenylpyridine(-1H))-iridium(III) hexafluorophosphate 作用下， 以 2,2,2-三氟乙醇 为溶剂， 反应 48.0h， 以39%的产率得到ethyl 1-allyl-3-hydroxy-2-oxoindoline-3-carboxylate
  参考文献：
  名称：

  Visible light mediated aerobic oxidative hydroxylation of 2-oxindole-3-carboxylate esters: an alternative approach to 3-hydroxy-2-oxindoles

  摘要：

  本文描述了一种便利的氧化氢化合成3-取代吲哚酮的方法，在温和的反应条件下完成。该过程通过在可见光照射下在光催化剂的存在下激活空气中的分子氧来实现。所需产物的产率高达89％，无需添加碱或化学氧化剂。

  DOI：

  10.1515/hc-2019-0114
• 作为产物：
  描述：

  1-烯丙基-1H-吲哚-2,3-二酮 在 sodium hydride 、 一水合肼 作用下， 以 甲苯 、 mineral oil 为溶剂， 反应 6.0h， 生成 1-Allyl-2-oxo-2,3-dihydro-1H-indole-3-carboxylic acid ethyl ester
  参考文献：
  名称：

  Oxidative Dimerization of 2-Oxindoles Promoted by KO^tBu-I₂: Total Synthesis of (±)-Folicanthine

  摘要：

  A transition-metal-free oxidative coupling of 2-oxindoles has been demonstrated in the presence of 1.2 equiv each of potassium tert-butoxide and iodine. The method yields a diverse range of structurally different homo- and heterodimerized 2-oxindoles bearing vicinal all-carbon quaternary centers of great synthetic importance. A radical-driven pathway has been tentatively proposed.

  DOI：

  10.1021/acs.orglett.5b00032

文献信息

• 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
• Stereoselective synthesis of C3-tetrasubstituted oxindoles <i>via</i> copper catalyzed asymmetric propargylation
  作者：Jiao-Mei Wang、Yu Zhao、Chang-Sheng Yao、Kai Zhang

  DOI：10.1039/d2ra04603b

  日期：——

  Herein, a copper catalyzed asymmetric propargylation of 2-oxindole-3-carboxylate esters with terminal propargylic esters is described. This strategy successfully provides a direct approach to constructing a broad range of chiral C3-tetrasubstituted oxindoles with contiguous tertiary and quaternary carbon stereocenters in high yields and excellent enantioselectivities (16 examples, up to 99% yield and

  本文描述了铜催化的 2-羟吲哚-3-羧酸酯与末端炔丙酸酯的不对称炔丙基化。该策略成功地提供了一种直接方法，以高产率和优异的对映选择性（16 个实例，高达 99% 产率和 98% ee）构建具有连续叔和季碳立构中心的广泛手性 C3-四取代羟吲哚。此外，两个新形成的立体中心的非对映异构体可以通过硅胶色谱分离，从而提供有价值的立体选择性获得C3-四取代羟吲哚的所有四种可能的立体异构体。
• 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.
• Efficient asymmetric Michael reaction of 2-oxindole-3-carboxylate esters with maleimides catalyzed by cinchonidine
  作者：Jing Zhou、Li-Na Jia、Lin Peng、Qi-Lin Wang、Fang Tian、Xiao-Ying Xu、Li-Xin Wang

  DOI：10.1016/j.tet.2014.03.065

  日期：2014.5

  A highly efficient enantioselective Michael reaction of 2-oxindole-3-carboxylate esters with N-maleimides catalyzed by commercially available cinchonidine was described. The desired adducts, containing a quaternary center at the C3-position and a vicinal tertiary center, were obtained in excellent yields (up to 99%), good enantioselectivities (up to 85% ee), and diastereoselectivities (dr>90:10) in the presence of 0.05-5 mol % catalyst loading. (C) 2014 Elsevier Ltd. All rights reserved.
• Oxidative Dimerization of 2-Oxindoles Promoted by KO^<i>t</i>Bu-I₂: Total Synthesis of (±)-Folicanthine
  作者：Santanu Ghosh、Saikat Chaudhuri、Alakesh Bisai

  DOI：10.1021/acs.orglett.5b00032

  日期：2015.3.20

  A transition-metal-free oxidative coupling of 2-oxindoles has been demonstrated in the presence of 1.2 equiv each of potassium tert-butoxide and iodine. The method yields a diverse range of structurally different homo- and heterodimerized 2-oxindoles bearing vicinal all-carbon quaternary centers of great synthetic importance. A radical-driven pathway has been tentatively proposed.