methyl 3-(1H-indol-3-yl)-acrylate | 2756-97-0

• 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: methyl 3-(1H-indol-3-yl)-acrylate
• 英文别名: methyl 3-(1H-indol-3-yl)prop-2-enoate
• CAS: 2756-97-0
• 化学式: C₁₂H₁₁NO₂
• 分子量: 201.225
• InChiKey: JKVXFZPEUCTHQO-UHFFFAOYSA-N

物化性质

• 沸点：
  387.1±17.0 °C(Predicted)
• 密度：
  1.235±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  42.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl 3-(1H-indol-3-yl)-acrylate 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以69%的产率得到3-(3-indolyl)-2-methoxycarbonyl-1-methoxycarbonylmethyl-1,2,3,4-tetrahydrocyclopent[b]indole
  参考文献：
  名称：

  Exploring stereoselectivity of 3-indolyl cyclopent[b]indoles: A parallel synthesis and anti-EGFR study on human cancer cells

  摘要：

  We synthesized a series of novel 3-indolyl cyclopent[b]indoles by trifluoroacetic acid mediated cyclodimerizations. The reaction showed high stereoselectivity and moderate to good yields. The influencing factors for stereoselectivity were systematically analyzed and a stepwise reaction mechanism was proposed. The cell viability tests in two colon and two lung cancer cell lines indicated the 1-benzyl-2phenyl-group in 3-indolyl cyclopent[b]indoles was critical for the observed lower IC(50)s in these compounds. Western blot analysis demonstrated that the compound inhibited the expression and phosphorylation of EGFR through altered HSP90 expression. Further cell cycle and cell cycle check point protein analyses showed expected anti-cellular proliferation and cell cycle arresting properties associated with suppressed EGFR expression and phosphorylation. These data revealed a novel molecular mechanism explaining the observed cytotoxicities for these compounds. (C) 2014 Elsevier Masson SAS. All rights reserved.

  DOI：

  10.1016/j.ejmech.2013.08.012
• 作为产物：
  描述：

  α-(3-indolyl) N-phenyl nitrone 在 palladium 10% on activated carbon 、 甲酸铵 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 0.08h， 生成 methyl 2-((1H-indol-3-yl)methyl)-3-hydroxypropanoate 、 methyl 3-(1H-indol-3-yl)-acrylate
  参考文献：
  名称：

  吲哚基-异唑烷的形成和还原性开环反应：获得新型天然产物类似物和前体

  摘要：

  的区域选择性和立体选择性的1,3-偶极环加成Ç - - （3-吲哚基）ñ -phenylnitrone（2用variedly取代dipolarophiles被执行以获得）顺式- C4和C5取代的吲哚基-异恶唑烷6A-C和7A-F， 分别。通过使用各种还原剂还原获得的异恶唑烷，会导致N–O键断裂，同时伴随C–N键断裂，从而导致形成基于吲哚的新型天然产物类似物和前体。

  DOI：

  10.1016/j.tet.2015.12.032

文献信息

• Palladium(II)-Catalyzed Regioselective Direct C2 Alkenylation of Indoles and Pyrroles Assisted by the<i>N</i>-(2-Pyridyl)sulfonyl Protecting Group
  作者：Alfonso García-Rubia、Ramón Gómez Arrayás、Juan C. Carretero

  DOI：10.1002/anie.200902802

  日期：2009.8.17

  N‐(2‐pyridyl)sulfonyl group controls the direct PdII‐catalyzed alkenylation of indoles, affording the corresponding products in good yields and with complete regiocontrol at C2 (see scheme, DMA=dimethylacetamide). The protocol was also extended to pyrrole derivatives. The final reductive desulfonylation affords the C2‐substituted indoles and pyrroles in good yields.

  易于穿脱：N-（2-吡啶基）磺酰基可控制Pd II催化的吲哚直接烯基化，提供相应的产物，收率良好，在C2处具有完全的区域控制能力（参见方案，DMA =二甲基乙酰胺）。该协议还扩展到吡咯衍生物。最终的还原性脱磺酰化反应可得到高收率的C2取代的吲哚和吡咯。
• PdII-Catalysed CH Functionalisation of Indoles and Pyrroles Assisted by the Removable N-(2-Pyridyl)sulfonyl Group: C2-Alkenylation and Dehydrogenative Homocoupling
  作者：Alfonso García-Rubia、Beatriz Urones、Ramón Gómez Arrayás、Juan Carlos Carretero

  DOI：10.1002/chem.201001126

  日期：2010.8.16

  The easily installed and removed N‐(2‐pyridyl)sulfonyl group exerts complete C2 regiocontrol over the PdII‐catalysed CH alkenylation of indoles and pyrroles, affording the corresponding products in good isolated yields (typically ≥70 %). A remarkable feature of this catalyst system is that it tolerates a wide variety of substituted alkenes, including conjugated electron‐deficient alkenes, styrenes

  的容易安装和移除ñ - （2-吡啶基）磺酰基施加完整C2区域控制在钯II -催化的Ç  ħ吲哚和吡咯，得到良好的分离产率（典型地≥70％）的相应的产品的烯基。该催化剂体系的显着特点是它可以耐受多种取代的烯烃，包括共轭电子不足的烯烃，苯乙烯和1,3-二烯以及共轭1,1和1,2-二取代的烯烃。最终的还原性脱磺酰化反应可得到高收率的C2取代的游离NH吲哚和吡咯。这个N（2-吡啶基）磺酰基导向策略也已扩展到吲哚分子间，脱氢均偶联的规程的开发，提供了2,2'-双吲哚。基于与同位素标记的起始原料反应的反应机理研究以及对各种电子底物的竞争动力学研究表明，存在螯合辅助的亲电子芳族取代palladation机制。
• Synthesis of 3-alkenylindoles through regioselective C–H alkenylation of indoles by a ruthenium nanocatalyst
  作者：Abhijit Paul、Debnath Chatterjee、Srirupa Banerjee、Somnath Yadav

  DOI：10.3762/bjoc.16.16

  日期：——

  3-Alkenylindoles are biologically and medicinally very important compounds, and their syntheses have received considerable attention. Herein, we report the synthesis of 3-alkenylindoles via a regioselective alkenylation of indoles, catalysed by a ruthenium nanocatalyst (RuNC). The reaction tolerates several electron-withdrawing and electron-donating groups on the indole moiety. Additionally, a “robustness screen” has also been employed to demonstrate the tolerance of several functional groups relevant to medicinal chemistry. With respect to the Ru nanocatalyst, it has been demonstrated that it is recoverable and recyclable up to four cycles. Also, the catalyst acts through a heterogeneous mechanism, which has been proven by various techniques, such as ICPMS and three-phase tests. The nature of the Ru nanocatalyst surface has also been thoroughly examined by various techniques, and it has been found that the oxides on the surface are responsible for the high catalytic efficiency of the Ru nanocatalyst.

  3-烯基吲哚是生物学和药学上非常重要的化合物，它们的合成受到了广泛关注。在这里，我们报告了通过钌纳米催化剂（RuNC）催化的吲哚的区域选择性烯基化合成3-烯基吲哚。该反应容忍吲哚基上的多种电子吸引和电子供体基团。此外，还采用了“稳健性筛选”来展示对药物化学相关的几种功能基团的耐受性。关于钌纳米催化剂，已经证明它可回收和循环使用高达四个周期。此外，催化剂通过异质机制起作用，这已通过各种技术（如ICPMS和三相测试）证明。还通过各种技术彻底研究了钌纳米催化剂表面的性质，并发现表面氧化物负责钌纳米催化剂的高催化效率。
• MOFs Extend the Lifetime of Pd(II) Catalyst for Room Temperature Alkenylation of Enamine-Like Arenes
  作者：Francisco G. Cirujano、Pedro Leo、Jannick Vercammen、Simon Smolders、Gisela Orcajo、Dirk E. De Vos

  DOI：10.1002/adsc.201800817

  日期：2018.10.18

  The synthesis of pharmaceutically relevant scaffolds, such as substituted indoles or uracils, through the alkenylation of the “enamine‐like” aromatic C−H bond is performed at room temperature using catalytic amounts of Pd(OAc)2 in the presence of redox active, stable and reusable metal‐organic microporous frameworks. This is the first time that redox/acid active sites in the porous, non‐toxic and earth

  在室温下，在氧化还原活性物质存在的情况下，使用催化量的Pd（OAc）2，通过“类烯胺”芳族CH键的烯基化反应合成药物相关的支架，例如取代的吲哚或尿嘧啶。稳定且可重复使用的金属有机微孔框架。这是首次在多孔，无毒且富含泥土的坚固MOF-74平台上使用氧化还原/酸活性位点，以避免在环境条件下工作的阳离子Pd物种快速失活。
• Pd(II) supramolecular cage-catalyzed successive oxidative coupling: One-pot and regioselective synthesis of functionalized carbazoles from indoles
  作者：Xi-Ren Wu、He-Long Peng、Lian-Qiang Wei、Li-Ping Li、Su-Yang Yao、Bao-Hui Ye

  DOI：10.1016/j.catcom.2019.02.023

  日期：2019.5

  compound in pharmaceuticals and functional materials. A new Pd(II) supramolecular cage-catalyzed protocol for the synthesis of multifunctional carbazoles from indoles is described through regioselective successive oxidative Heck reactions. This new protocol is highly efficient, with a low Pd (2.4 mol%) catalyst loading and good compatibility for both N-H free and N-protected indole substrates. Moreover, it

  咔唑是药物和功能材料中的重要化合物。通过区域选择性连续氧化Heck反应描述了一种新的Pd（II）超分子笼催化的方案，用于从吲哚合成多功能咔唑。该新方案非常高效，具有低Pd（2.4 mol％）的催化剂负载量，并且对无NH和受N保护的吲哚底物都具有良好的相容性。而且，它可以通过一锅两步法用于合成具有各种官能团的咔唑。优异的催化活性可以归因于超分子笼状结构在笼状表面上均匀分布和定义明确的Pd（II）活性中心中的独特特性。