ethyl 3-benzyl-1-methyl-2-oxoindoline-3-carboxylate | 14750-27-7

• 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 3-benzyl-1-methyl-2-oxoindoline-3-carboxylate
• 英文别名: Ethyl-3-benzyl-1-methyl-2-oxoindoline-3-carboxylate；ethyl 3-benzyl-1-methyl-2-oxoindole-3-carboxylate
• CAS: 14750-27-7
• 化学式: C₁₉H₁₉NO₃
• 分子量: 309.365
• InChiKey: UPBMAPBVIWHNRR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  丙二酸单乙酯 在 potassium tert-butylate 、 碘 、 三乙胺 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 0.75h， 生成 ethyl 3-benzyl-1-methyl-2-oxoindoline-3-carboxylate
  参考文献：
  名称：

  通过sp（2）CH和sp（3）CH键的“无过渡金属”分子内脱氢偶联（IDC）合成2-氧吲哚。

  摘要：

  经由“无过渡金属”的分子内脱氢偶联（IDC），已经完成了在假苄基位置带有全碳季中心的各种2-氧吲哚的合成。通过使用KOt-Bu催化β-N-芳基酰胺酯与烷基卤化物的一锅C-烷基化，然后脱氢偶联，通过形成碳-碳键来进行2-氧吲哚部分的构建。实验证据表明该反应朝向自由基介导的途径。

  DOI：

  10.3762/bjoc.12.111

文献信息

• Low-Temperature, Transition-Metal-Free Cross-Dehydrogenative Coupling Protocol for the Synthesis of 3,3-Disubstituted Oxindoles
  作者：James R. Donald、Richard J. K. Taylor、Wade F. Petersen

  DOI：10.1021/acs.joc.7b02085

  日期：2017.10.20

  strong, nonreversible base in these reactions has been found to effect a dramatic drop in reaction temperature (to room temperature) relative to the current state-of-the-art (>100 °C) procedure. When employing iodine as an “oxidant”, new evidence suggests that this transformation may occur via a transiently stable iodinated intermediate rather than by direct single-electron oxidation.

  报道了一种通过交叉脱氢偶联（CDC）合成3,3-二取代的2-氧吲哚的新的低温程序。已经发现在这些反应中使用强的，不可逆的碱会导致反应温度相对于当前的最新技术水平（> 100°C）急剧下降（降至室温）。当使用碘作为“氧化剂”时，新证据表明，这种转变可能是通过暂时稳定的碘化中间体而不是直接的单电子氧化而发生的。
• Oxindole synthesis by direct C–H, Ar–H coupling
  作者：Alexis Perry、Richard J. K. Taylor

  DOI：10.1039/b903516h

  日期：——

  A novel copper(II)-mediated route for the conversion of anilides into 3,3-disubstituted-oxindoles is described which proceeds via a formal C–H, Ar–H coupling process.

  描述了一种新颖的铜(II)介导的路线，可以将氨基取代的苯酰胺转化为3,3-二取代的氧吲哚，该过程通过形式上的C–H与芳基–H偶联反应进行。
• Atom economical synthesis of oxindoles by metal-catalyzed intramolecular C–C bond formation under solvent-free and aerobic conditions
  作者：Se In Son、Won Koo Lee、Jieun Choi、Hyun-Joon Ha

  DOI：10.1039/c5gc00703h

  日期：——

  Diversely substituted oxindoles were obtained from atom economical direct C-C bond formation reactions of various substituted anilides and pyridinylamides with metal salts as catalysts including Cu2O, FeCl3, Fe2O3, TiO2, ZnO,...

  各种取代的苯甲酸酯和吡啶基酰胺与金属盐作为催化剂的原子经济的直接CC键形成反应，获得了不同取代的羟吲哚，其中金属盐包括Cu2O，FeCl3，Fe2O3，TiO2，ZnO，...
• Di-tert-butyl peroxide (DTBP) promoted dehydrogenative coupling: an expedient and metal-free synthesis of oxindoles via intramolecular C(sp²)–H and C(sp³)–H bond activation
  作者：Biplab Mondal、Brindaban Roy

  DOI：10.1039/c5ra09055e

  日期：——

  An efficient di-tert-butyl peroxide (DTBP) promoted synthesis of oxindole has been developed. This methodology involves C(sp3)–H and C(sp2)–H bond activation under metal-free conditions. This synthetic approach towards oxindole synthesis avoids bases and hazardous iodine reagents unlike other methodologies developed so far. This metal- and base-free protocol is operationally simple and ecofriendly

  已经开发了一种有效的过氧化二叔丁基（DTBP）促进的羟吲哚合成方法。该方法涉及在无金属条件下活化C（sp 3）–H和C（sp 2）–H键。与迄今为止开发的其他方法不同，这种合成羟吲哚的合成方法避免了碱和有害碘试剂的使用。这种无金属和无碱的协议操作简单，环保。它提供了一种在110°C的DCE中以中等到非常高的收率获得吲哚的简便方法。
• Quantitative Evaluation of C–H···O and C–H···π Intermolecular Interactions in Ethyl-3-benzyl-1-methyl-2-oxoindoline-3-carboxylate and 3-Methyl-but-2-en-1-yl-1,3-dimethyl-2-oxoindoline-3-carboxylate: Insights from PIXEL and Hirshfeld Analysis
  作者：Dhananjay Dey、Santanu Ghosh、Deepak Chopra

  DOI：10.1007/s10870-014-0492-8

  日期：2014.3

  The X-ray crystallographic structures of two biologically active molecules, namely (±)-ethyl-3-benzyl-1-methyl-2-oxoindoline-3-carboxylate (I) and (±)-3-methyl-but-2-en-1-yl-1,3-dimethyl-2-oxoindoline-3-carboxylate (II) have been investigated based on the molecular conformation and supramolecular packing of the molecules in the solid state. These two structures assemble via C–H···O=C and C–H···π intermolecular interactions which contribute towards the stability of the crystal packing. In order to gain quantitative insights into the nature of non-covalent interaction between different molecules the interaction energy of the molecular pairs obtained after analysis of the crystal structures for both the molecules has been performed by using the PIXEL approach along with high level DFT+Disp calculations. Hirshfeld surface analysis and the associated fingerprint plots provide rapid quantitative insight into the intermolecular interactions in molecular solids. This article provides support to the fact that every molecule can be explored in detail for an understanding of its solid state structure via experimental and computational tools in crystal engineering. This manuscript outlines the significance (nature and energetic) of weak intermolecular interactions in ethyl-3-benzyl-1-methyl-2-oxoindoline-3-carboxylate and 3-methyl-but-2-en-1-yl-1,3-dimethyl-2-oxoindoline-3-carboxylate in the solid state (using PIXEL) and comparison with that in the gas phase (using TURBOMOLE) and their partitioning into coulombic, polarization, dispersive and repulsive components. Furthermore, Hirshfeld surface analysis has also been used to probe such intermolecular interactions.

  基于分子构象和固态分子超分子堆积，对两种生物活性分子（即（±）-乙基-3-苄基-1-甲基-2-氧代吲哚啉-3-羧酸（I）和（±）-3-甲基-丁-2-烯-1-基-1,3-二甲基-2-氧代吲哚啉-3-羧酸（II））的X射线晶体结构进行了研究。这两种结构通过C-H·O=C和C-H·π分子间相互作用组装，从而有助于晶体堆积的稳定性。为了定量了解不同分子之间非共价相互作用的性质，使用PIXEL方法以及高级别DFT+Disp计算对两种分子的晶体结构进行分析后，获得了分子对的相互作用能。Hirshfeld表面分析和相关的指纹图谱能够快速定量了解分子固体中的分子间相互作用。本文通过晶体工程中的实验和计算工具，详细研究了每个分子，以了解其固态结构。本文概述了（±）-乙基-3-苄基-1-甲基-2-氧代吲哚啉-3-羧酸和（±）-3-甲基-丁-2-烯-1-基-1,3-二甲基-2-氧代吲