3-(thiophen-3-yl)benzo[b]thiophene

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 双噻吩和低聚噻吩
• 英文名称: 3-(thiophen-3-yl)benzo[b]thiophene
• 英文别名: 3-thiophen-3-yl-1-benzothiophene
• 化学式: C₁₂H₈S₂
• 分子量: 216.328
• InChiKey: RTOHTQLPWLDLPG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3-碘噻吩 、 苯并噻吩 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 六氟异丙醇 、 三(4-甲氧苯基)膦 、 silver carbonate 作用下， 反应 16.0h， 以63%的产率得到3-(thiophen-3-yl)benzo[b]thiophene
  参考文献：
  名称：

  噻吩和苯并 [b] 噻吩的室温直接 β-芳基化以及 Heck 型通路的动力学证据

  摘要：

  报道了苯并[b]噻吩和噻吩在室温下以芳基碘作为偶联伙伴的区域选择性β-芳基化的第一个例子。这种方法因其操作简单而突出：不需要任何一种起始材料的预官能化，反应对空气和水分不敏感，并且在室温下进行。温和的条件提供了广泛的官能团耐受性，通常具有完全的区域选择性和高产率，从而形成高效的催化系统。包括 13C 和 2H KIE 在内的初步机理研究表明，该过程是通过噻吩双键上的协同碳钯化作用发生的，然后是碱基辅助的抗消除作用。

  DOI：

  10.1021/jacs.5b12242

文献信息

• A General Synthesis of Diarylketones by Means of a Three-Component Cross-Coupling of Aryl and Heteroaryl Bromides, Carbon Monoxide, and Boronic acids
  作者：Helfried Neumann、Anne Brennführer、Matthias Beller

  DOI：10.1002/chem.200800001

  日期：2008.4.18

  Pd(OAc)2/di-1-adamantyl-n-butylphosphine (cataCXium A) is highly active in the three-component Suzuki carbonylation and represents the most general catalyst system reported up to now. A broad range of aryl/heteroaryl bromides and aryl boronic acids can be coupled to the corresponding diarylketones at low catalyst loadings.

  Pd（OAc）2 /二-1-金刚烷基-正丁基膦（cataCXium A）在三组分铃木羰基化反应中具有很高的活性，是迄今为止报道的最通用的催化剂体系。各种各样的芳基/杂芳基溴化物和芳基硼​​酸可以在低催化剂负载下与相应的二芳基酮偶联。
• Synthesis of Functionalized Carbon-Sulfur [5]Helicene: Pd-Catalyzed Negishi Cross-Coupling Between the β-Positions of Thiophenes
  作者：Andrzej Rajca、Makoto Miyasaka

  DOI：10.1055/s-2003-43335

  日期：——

  Octyl- and bromo-substituted carbon-sulfur [5]helicene was prepared in several steps starting from either thiophene or 3-bromothiophene. Pd-catalyzed Negishi cross-coupling between the β-positions of thiophenes was one of the key steps in the synthesis.

  从噻吩或 3-溴噻吩开始，通过几个步骤制备了辛基和溴代碳硫 [5] 螺旋烯。噻吩δ-位之间的钯催化内吉西交叉偶联是合成的关键步骤之一。
• Reusable, Highly Active Heterogeneous Palladium Catalyst by Convenient Self-Encapsulation Cross-Linking Polymerization for Multiple CarbonCarbon Cross-Coupling Reactions at ppm to ppb Palladium Loadings
  作者：Zhongmin Dong、Zhibin Ye

  DOI：10.1002/adsc.201400520

  日期：2014.11.3

  AbstractDesigning reusable high‐performance heterogeneous palladium (Pd) catalysts via convenient, economic synthesis is of great importance to the industrial applications of various carbon‐carbon cross‐coupling reactions. We demonstrate herein a convenient one‐pot self‐encapsulation synthesis of a heterogeneous Pd catalyst [Pd@PDEB, PDEB=poly(1,3‐diethynylbenzene)] directly from commercially available, economic precursors. In the synthesis, the formation of the cross‐linked polymer networks and Pd encapsulation are accomplished simultaneously, turning a homogeneous Pd polymerization catalyst into the heterogeneous cross‐coupling catalyst. As a unique, practical heterogeneous catalyst, Pd@PDEB shows remarkably high activity, high reusability, and high versatility towards at least four types of cross‐coupling reactions (Suzuki–Miyaura, Stille, allylic arylation, and Mizoroki–Heck reactions) with even difficult reactants (aryl chlorides and heteroaryl halides) under aerobic conditions with Pd loadings down to ppm or even ppb levels. Evidences from hot filtration and 3‐phase tests demonstrate the heterogeneous nature of the catalyst with very low Pd leaching and negligible contributions of leached homogeneous Pd species towards the coupling reactions.magnified image
• Micellar Catalysis of Suzuki−Miyaura Cross-Couplings with Heteroaromatics in Water
  作者：Bruce H. Lipshutz、Alexander R. Abela

  DOI：10.1021/ol801712e

  日期：2008.12.4

  Pd-catalyzed couplings involving several heteroaromatic halides (bromides and chlorides) as well as boronic acids can be done under exceedingly mild conditions (between rt and 40 degrees C) in pure water using commercially available Pd catalysts and PTS, a nanomicelle-forming amphiphile.
• Room-Temperature Direct β-Arylation of Thiophenes and Benzo[<i>b</i>]thiophenes and Kinetic Evidence for a Heck-type Pathway
  作者：Chiara Colletto、Saidul Islam、Francisco Juliá-Hernández、Igor Larrosa

  DOI：10.1021/jacs.5b12242

  日期：2016.2.10

  The first example of a regioselective β-arylation of benzo[b]thiophenes and thiophenes at room temperature with aryl iodides as coupling partners is reported. This methodology stands out for its operational simplicity: no prefunctionalization of either starting material is required, the reaction is insensitive to air and moisture, and it proceeds at room temperature. The mild conditions afford wide

  报道了苯并[b]噻吩和噻吩在室温下以芳基碘作为偶联伙伴的区域选择性β-芳基化的第一个例子。这种方法因其操作简单而突出：不需要任何一种起始材料的预官能化，反应对空气和水分不敏感，并且在室温下进行。温和的条件提供了广泛的官能团耐受性，通常具有完全的区域选择性和高产率，从而形成高效的催化系统。包括 13C 和 2H KIE 在内的初步机理研究表明，该过程是通过噻吩双键上的协同碳钯化作用发生的，然后是碱基辅助的抗消除作用。