1-methyl-3-(3'-methylpent-3'-enyl)indole | 596105-25-8

• 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-methyl-3-(3'-methylpent-3'-enyl)indole
• 英文别名: N-methyl-3-(3-methyl-3-pentenyl)indole；methyl-3-(3-methylpent-3-en-1-yl)-1H-indole；(Z/E)-1-methyl-3-(3-methylpent-3-enyl)indole；(E/Z)-1-methyl-3-(3-methylpent-3-enyl)indole；1-Methyl-3-(3-methylpent-3-enyl)indole
• CAS: 596105-25-8
• 化学式: C₁₅H₁₉N
• 分子量: 213.323
• InChiKey: DKQSFUBZMBDDNU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  4.9
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-methyl-3-(3'-methylpent-3'-enyl)indole 在 ruthenium trichloride silver trifluoromethanesulfonate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 12.0h， 以40%的产率得到3-Ethyl-3,4-dimethyl-1,2,3,4-tetrahydro-cyclopenta[b]indole
  参考文献：
  名称：

  Ru(III)-Catalyzed Cyclization of Arene-Alkene Substrates via Intramolecular Electrophilic Hydroarylation

  摘要：

  We herein report that RuCl3/AgOTf has proven to be a hydroarylation catalyst with an efficiency and scope superior to previously known methods. This catalyst demonstrated consistent performance with arene-ene substrates of diverse structural features, providing good to excellent yields of cyclization products (chromanes, tetralins, terpenoids, dihydrocoumarins).

  DOI：

  10.1021/ol036385i
• 作为产物：
  描述：

  4-(1H-吲哚-3-基)丁烷-2-酮 在 potassium tert-butylate 、 sodium hydride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 7.25h， 生成 1-methyl-3-(3'-methylpent-3'-enyl)indole
  参考文献：
  名称：

  Catalytic C−H Bond Functionalization with Palladium(II):  Aerobic Oxidative Annulations of Indoles

  摘要：

  A palladium-catalyzed aerobic oxidative annulation of indoles is described. We have demonstrated that a variety of factors influence these cyclizations, and in particular the electronic nature of the pyridine ligand is crucial. It is also remarkable that these oxidative cyclizations can proceed in good yield despite background oxidative decomposition pathways, testament to the facile nature with which molecular oxygen can serve as the direct oxidant for Pd(0). We have also shown that the mechanism most likely involves initial indole palladation (formal C-H bond activation) followed by migratory insertion and beta-hydrogen elimination.

  DOI：

  10.1021/ja035054y

文献信息

• Enantioselective Fujiwara-Moritani Indole and Pyrrole Annulations Catalyzed by Chiral Palladium(II)-NicOx Complexes
  作者：Julia A. Schiffner、Thorsten H. Wöste、Martin Oestreich

  DOI：10.1002/ejoc.200901129

  日期：2010.1

  catalytic asymmetric Fujiwara-Moritani ring closures of several indole- and pyrrole-based cyclization precursors are reported. These unprecedented oxidative palladium(II)-catalyzed annulations allow for the formation of a stereogenic quaternary carbon atom, and decent levels of enantiocontrol are seen in 5-exo-trig cyclizations (54 % ee for an indole and 76 % ee for a pyrrole) while 6-exo-trig ring

  报道了几种基于吲哚和吡咯的环化前体的催化不对称 Fujiwara-Moritani 闭环。这些前所未有的氧化钯 (II) 催化环化允许形成立体季碳原子，并且在 5-exo-trig 环化（吲哚 54 % ee 和吡咯 76 % ee）中看到了相当水平的对映控制而 6-exo-trig 闭环提供了基本上外消旋的材料。具有尼古丁平台 (NicOx) 的新型恶唑啉配体对于良好的催化转化至关重要，因为传统的 PyOx 配体无法产生可接受的化学产率。详细描述了这些 NicOx 配体的制备以及环化前体的合成。
• Highly Efficient Construction of Benzene Ring in Carbazoles by Palladium-Catalyzed <i>endo</i>-Mode Oxidative Cyclization of 3-(3‘-Alkenyl)indoles
  作者：Aidi Kong、Xiuling Han、Xiyan Lu

  DOI：10.1021/ol060039u

  日期：2006.3.1

  [reaction: see text] A highly efficient construction of the benzene ring in carbazoles by palladium-catalyzed endo-mode oxidative cyclization of 3-(3'-alkenyl)indoles was developed. The reaction utilizes benzoquinone as the stoichiometric oxidant and is conducted under mild conditions.

  [反应：见正文]通过3-（3'-烯基）吲哚的钯催化内模氧化环化，开发了咔唑中苯环的高效结构。该反应利用苯醌作为化学计量的氧化剂，并且在温和的条件下进行。
• Enantioselective synthesis of tetrahydrocyclopenta[b]indole bearing a chiral quaternary carbon center via Pd(<scp>ii</scp>)–SPRIX-catalyzed C–H activation
  作者：Mohamed Ahmed Abozeid、Shiho Sairenji、Shinobu Takizawa、Makoto Fujita、Hiroaki Sasai

  DOI：10.1039/c7cc03199h

  日期：——

  conjunction with the chiral spiro bis(isoxazoline) ligand (SPRIX). The presence of an N-allyl substituent on the substrate has a strong impact on both reactivity and selectivity, leading to tricyclic indole products (up to 96% ee) with a chiral quaternary carbon center.

  通过Pd（OCOCF 3）2和手性螺双（异恶唑啉）配体（SPRIX）建立了通过C–H活化的3-烯基吲哚的高对映选择性环化反应。底物上N-烯丙基取代基的存在对反应性和选择性都有很强的影响，导致具有手性季碳中心的三环吲哚产物（至多96％ee）。
• A Catalytic Asymmetric Fujiwara-Moritani Cyclization
  作者：Martin Oestreich、Julia Schiffner、Axel Machotta

  DOI：10.1055/s-2008-1078271

  日期：——

  An enantioselective intramolecular Fujiwara-Moritani reaction involving direct C-H functionalization using modified PyOX ligands is reported for the first time. Screening of several ligand-oxidant combinations eventually produced a stereogenic quaternary carbon with promising enantiocontrol (54% ee) and in good chemical yield (71%).

  首次报道了使用改良的PyOX配体进行分子内藤原-森谷反应，该反应涉及直接C-H官能化。通过筛选几种配体-氧化剂组合，最终获得了具有良好对映体控制（54% ee）和化学产率（71%）的立体四元碳。
• C–H bond functionalizations with palladium(II): intramolecular oxidative annulations of arenes
  作者：Eric M. Ferreira、Haiming Zhang、Brian M. Stoltz

  DOI：10.1016/j.tet.2008.01.052

  日期：2008.6

  Oxidative annulations for the synthesis of carbocycles were developed using a catalytic palladium(II) system. Indoles with pendant olefin tethers were oxidatively cyclized to form annulated products. Electron-rich aromatic systems were also investigated, culminating in the synthesis of benzofurans and dihydrobenzofurans by a similar protocol. These reactions were demonstrated to proceed by an initial

  使用催化钯 (II) 系统开发了用于合成碳环的氧化环。具有侧链烯烃系链的吲哚被氧化环化以形成环状产物。还研究了富含电子的芳香系统，最终通过类似的协议合成苯并呋喃和二氢苯并呋喃。这些反应被证明是通过初始 CH 键官能化事件进行的，然后是烯烃插入和 β-氢化物消除。