3-methylbut-2-en-1-yl 3-(methyl(phenyl)amino)-3-oxopropanoate | 1410940-49-6

• 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: 3-methylbut-2-en-1-yl 3-(methyl(phenyl)amino)-3-oxopropanoate
• CAS: 1410940-49-6
• 化学式: C₁₅H₁₉NO₃
• 分子量: 261.321
• InChiKey: XHDDQXFDEHYKGN-UHFFFAOYSA-N

物化性质

• 沸点：
  379.2±25.0 °C(Predicted)
• 密度：
  1.102±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.55
• 重原子数：
  19.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  46.61
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  3-methylbut-2-en-1-yl 3-(methyl(phenyl)amino)-3-oxopropanoate 在 potassium tert-butylate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二甲基亚砜 为溶剂， 生成 (±)-3-methylbut-2-en-1-yl 3-benzyl-1-methyl-2-oxoindoline-3-carboxylate
  参考文献：
  名称：

  DDQ-mediated Direct Intramolecular-Dehydrogenative-Coupling (IDC): Expeditious Approach to the Tetracyclic Core of Ergot Alkaloids

  摘要：

  An efficient route to 2-oxindoles bearing an all-carbon quaternary center at the pseudobenzylic position has been developed via a DDQ-mediated Intramolecular-Dehydrogenative-Coupling (IDC). The methodology involves a one-pot C-alkylation of beta-N-arylamido esters (7) concomitant with dehydrogenative-coupling in the presence of stoichiometric amount of DDQ. A tentative mechanistic route has been proposed for the oxidative coupling. The methodology provides a two-step entry to the ergoline structure of ergot alkaloids.

  DOI：

  10.1021/ol400899e
• 作为产物：
  描述：

  异戊烯醇 在 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 0.08h， 生成 3-methylbut-2-en-1-yl 3-(methyl(phenyl)amino)-3-oxopropanoate
  参考文献：
  名称：

  Intramolecular Dehydrogenative Coupling of sp² C–H and sp³ C–H Bonds: An Expeditious Route to 2-Oxindoles

  摘要：

  An intramolecular-dehydrogenative-coupling (IDC) using "transition-metal-free" oxidation conditions has been achieved to synthesize a variety of 2-oxindoles bearing an all-carbon quaternary stereogenic center at the benzylic position. The methodology involves a one-pot C-alkylation of beta-N-arylamido esters (3, 6) with alkyl halides using potassium tert-butoxide concomitant with a dehydrogenative coupling. A radical-mediated pathway has been tentatively proposed for the oxidative process.

  DOI：

  10.1021/ol302767w

文献信息

• Synthesis of 2-oxindoles via 'transition-metal-free' intramolecular dehydrogenative coupling (IDC) of sp² C–H and sp³ C–H bonds
  作者：Nivesh Kumar、Santanu Ghosh、Subhajit Bhunia、Alakesh Bisai

  DOI：10.3762/bjoc.12.111

  日期：——

  benzylic position has been achieved via a 'transition-metal-free' intramolecular dehydrogenative coupling (IDC). The construction of 2-oxindole moieties was carried out through formation of carbon-carbon bonds using KOt-Bu-catalyzed one pot C-alkylation of beta-N-arylamido esters with alkyl halides followed by a dehydrogenative coupling. Experimental evidences indicated toward a radical-mediated path for

  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。
• 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