4-(6-氯-1H-吲哚-3-基)丁烷-2-酮 | 596105-56-5

• 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
• 中文名称: 4-(6-氯-1H-吲哚-3-基)丁烷-2-酮
• 英文名称: 4-(6-chloro-1H-indol-3-yl)butan-2-one
• CAS: 596105-56-5
• 化学式: C₁₂H₁₂ClNO
• 分子量: 221.686
• InChiKey: UFKGBYROJGTBSW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  32.9
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-(6-氯-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 5.75h， 生成 6-Chloro-1-methyl-3-((E)-3-methyl-pent-3-enyl)-1H-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
• 作为产物：
  描述：

  6-氯吲哚 、 4-羟基-2-丁酮 在 tris(pentafluorophenyl)borane hydrate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 24.0h， 以70%的产率得到4-(6-氯-1H-吲哚-3-基)丁烷-2-酮
  参考文献：
  名称：

  β-羟基酮为MVK前体的硼催化芳烃的脱水Friedel-Crafts烷基化反应

  摘要：

  首次开发了硼催化的对环境有益的脱水吲哚/吡咯和苯胺衍生物与β-羟基酮的Friedel-Crafts烷基化反应。该方法可通过更安全，更便宜的β-羟基酮高效，绿色地替代有毒和不稳定的甲基乙烯基酮（MVK）。该反应具有易于操作，底物范围广且显着的特点，只有水是副产物。

  DOI：

  10.1002/adsc.202001269

文献信息

• Ruthenium-Catalyzed Selective C−C Coupling of Allylic Alcohols with Free Indoles: Influence of the Metal Catalyst
  作者：Ying-Qi Xia、Chao Li、Man Liu、Lin Dong

  DOI：10.1002/chem.201706080

  日期：2018.4.11

  Versatile reactive activities of allyl alcohols with free indoles in C-H functionalization reactions were investigated. Direct alkylation or cascade cyclization reactions could be selectively controlled based on the catalyst system: Ru(PPh3 )3 Cl2 provided C3-substituted β-ketone indoles whereas [Ru(p-cymene)Cl2 ]2 yielded cyclized indoles.

  研究了烯丙醇与游离吲哚在CH功能化反应中的多种反应活性。可以基于催化剂体系选择性地控制直接烷基化或级联环化反应：Ru（PPh3）3Cl2提供C3取代的β-酮吲哚，而[Ru（p-cymene）Cl2] 2则产生环化吲哚。
• 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）。
• Regioselective Cope Rearrangement and Prenyl Transfers on Indole Scaffold Mimicking Fungal and Bacterial Dimethylallyltryptophan Synthases
  作者：Karthikeyan Thandavamurthy、Deepti Sharma、Suheel K. Porwal、Dale Ray、Rajesh Viswanathan

  DOI：10.1021/jo501651z

  日期：2014.11.7

  rearrangement between C3 and C4 positions. Biomimetic conditions are reported that effect a [3,3]-sigmatropic shift whose two-step process is interrogated for intramolecularity and rate-limiting general base-promoted mechanism. Solvent polarity serves a crucial role in changing the regioselectivity, resulting in sole [1,3]-shifts under decalin. An intermolecular variant is also reported that effectively prenylates

  芳香异戊二烯基转移酶是一种活跃开采的酶类，其生物合成库正在增长。吲哚异戊二烯基转移酶催化各种异戊烯化色氨酸和二酮哌嗪的形成，导致形成具有高生物活性的真菌毒素。从根本上讲，l的C4异戊烯化机理-色氨酸最近浮出水面，引起了关于“直接”亲电烷基化机制（针对wt DMATS和FgaPT2）与吲哚C3-C4“应对”重排与随后的重新瘤化（针对突变体FgaPT2）之间的争论。本文中，我们为C3和C4位置之间的Cope重排提供了第一系列的区域选择性可调条件。据报道，仿生条件会影响[3,3]-σ转变，其两步过程被询问分子内和限速一般碱基促进机制。溶剂极性在改变区域选择性中起着至关重要的作用，导致十氢化萘下的唯一[1,3]位移。还报道了一种分子间变体，该变体有效地使l的C3位置异戊二烯化。-色氨酸，产生模仿细菌吲哚异戊二烯基转移酶进入的结构的产物。我们报告了一项详尽的研究，其中包括筛选各种取代基，并通过合成上
• Catalytic C−H Bond Functionalization with Palladium(II):  Aerobic Oxidative Annulations of Indoles
  作者：Eric M. Ferreira、Brian M. Stoltz

  DOI：10.1021/ja035054y

  日期：2003.8.1

  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.
• Boron‐Catalyzed Dehydrative Friedel‐Crafts Alkylation of Arenes Using <i>β</i> ‐Hydroxyl Ketone as MVK Precursor
  作者：Htet Htet San、Jie Huang、Seinn Lei Aye、Xiang‐Ying Tang

  DOI：10.1002/adsc.202001269

  日期：2021.4.27

  Boron‐catalyzed environmentally benign dehydrative Friedel‐Crafts alkylation of indole/pyrrole and aniline derivatives with β‐hydroxyl ketones has been developed for the first time. This method provides an efficient and green replacement of toxic and unstable methyl vinyl ketone (MVK) by safer and cheaper β‐hydroxyl ketone. The reaction features easy operation, wide substrate scope and significantly, only water

  首次开发了硼催化的对环境有益的脱水吲哚/吡咯和苯胺衍生物与β-羟基酮的Friedel-Crafts烷基化反应。该方法可通过更安全，更便宜的β-羟基酮高效，绿色地替代有毒和不稳定的甲基乙烯基酮（MVK）。该反应具有易于操作，底物范围广且显着的特点，只有水是副产物。