1-(1,2-dicarba-closo-dodecaboran-1-yl)naphthalene | 63697-33-6

• 英文名称: 1-(1,2-dicarba-closo-dodecaboran-1-yl)naphthalene
• 英文别名: 1-(1-naphthalenyl)-1,2-dicarba-closo-dodecaborane
• CAS: 63697-33-6
• 化学式: C₁₂H₁₈B₁₀
• 分子量: 270.385
• InChiKey: AYENJQAJUIDFCP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  1-(1,2-dicarba-closo-dodecaboran-1-yl)naphthalene 、 对氟硝基苯 在 potassium tert-butylate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以90%的产率得到1-(1-naphthyl)-2-(4-nitrophenyl)-o-carborane
  参考文献：
  名称：

  1,2-Dicarba-closo-dodecaboran-1-yl Naphthalene Derivatives

  摘要：

  1,2-Dicarba-closo-dodecaboranes (o-carboranes) and naphthalenes have potential value as components or building blocks for supramolecular systems, We have efficiently synthesized 1-(1,2-dicarba-closo-dodecaboran-1-yl) naphthalene and 2-(1,2-dicarba-closo-dodecaboran-1-yl) naphthalene derivatives by employing three preparative methods: cyclization of the corresponding acetylenes with decaborane(14), an Ullmann-type coupling reaction of carboranes with aryl halide, and the aromatic nucleophilic substitution (SNAr) reaction of aryl-o-carboranes with nitrophenyl halide, The optimum conditions of each method for synthesis of the title compounds were also investigated.

  DOI：

  10.1021/ic0509736
• 作为产物：
  描述：

  癸硼烷 、 1-乙炔基萘 在 乙硫醚 作用下， 以 甲苯 为溶剂， 以30%的产率得到1-(1,2-dicarba-closo-dodecaboran-1-yl)naphthalene
  参考文献：
  名称：

  1,2-Dicarba-closo-dodecaboran-1-yl Naphthalene Derivatives

  摘要：

  1,2-Dicarba-closo-dodecaboranes (o-carboranes) and naphthalenes have potential value as components or building blocks for supramolecular systems, We have efficiently synthesized 1-(1,2-dicarba-closo-dodecaboran-1-yl) naphthalene and 2-(1,2-dicarba-closo-dodecaboran-1-yl) naphthalene derivatives by employing three preparative methods: cyclization of the corresponding acetylenes with decaborane(14), an Ullmann-type coupling reaction of carboranes with aryl halide, and the aromatic nucleophilic substitution (SNAr) reaction of aryl-o-carboranes with nitrophenyl halide, The optimum conditions of each method for synthesis of the title compounds were also investigated.

  DOI：

  10.1021/ic0509736

文献信息

• Palladium-Catalyzed Direct Cross-Coupling of Carboranyllithium with (Hetero)Aryl Halides
  作者：Ju-You Lu、Hong Wan、Jianwei Zhang、Zhixuan Wang、Yang Li、Yongmei Du、Chunying Li、Zhao-Tie Liu、Zhong-Wen Liu、Jian Lu

  DOI：10.1002/chem.201603967

  日期：2016.12.5

  A palladium‐catalyzed direct C‐arylation reaction of readily available cage carboranyllithium reagents with aryl halides has been developed for the first time. This method is applicable to a wide range of aryl halide substrates including aryl iodides, aryl bromides, and heteroaromatic halides.

  首次开发了易于获得的笼式碳硼烷基锂试剂与芳基卤化物的钯催化直接C-芳基化反应。该方法适用于多种芳基卤化物底物，包括芳基碘化物，芳基溴化物和杂芳族卤化物。
• Improved synthesis of icosahedral carboranes containing exopolyhedral B C and C C bonds
  作者：Kierstyn P. Anderson、Harrison A. Mills、Chantel Mao、Kent O. Kirlikovali、Jonathan C. Axtell、Arnold L. Rheingold、Alexander M. Spokoyny

  DOI：10.1016/j.tet.2018.11.040

  日期：2019.1

  this method is tolerant towards alkyl-based Grignard reagents containing β-hydrogens. Furthermore, a transition metal-free approach to the substitution of carborane C-vertices with (hetero)aryl substrates has been developed under nucleophilic aromatic substitution (SNAr) conditions. The selective substitution of carboranes afforded by these methods holds potential for the rational synthesis of heterofunctionalized

  碳硼烷是富含硼的分子簇，具有电子特性，可通过正交方法进行顶点选择性修饰。我们报告了改进的功能化方法，利用正交化学在碳硼烷的富电子B顶点和贫电子C顶点处实现有效取代。通过使用具有富电子联芳基膦配体的钯基预催化剂，可以改善使用相应的格氏试剂在烷基和（杂）芳基上形成B顶点的功能，从而缩短了反应时间。重要的是，该方法对含有β-氢的基于烷基的格氏试剂具有耐受性。此外，在亲核芳香族取代（SNAr）条件下，已经开发出一种无过渡金属的方法用（杂）芳基底物取代碳硼烷C顶点。这些方法提供的碳硼烷的选择性取代具有合理合成在硼和碳基顶点上均带有取代基的杂官能化硼簇的潜力。
• Light-promoted copper-catalyzed cage C-arylation of <i>o</i>-carboranes: facile synthesis of 1-aryl-<i>o</i>-carboranes and <i>o</i>-carborane-fused cyclics
  作者：Hangcheng Ni、Zhenpin Lu、Zuowei Xie

  DOI：10.1039/d0nj02029j

  日期：——

  Light-promoted, copper catalyzed cage C–H arylation of o-carboranes with aryl halides has been achieved, leading to the facile synthesis of a variety of 1-aryl-o-carboranes and o-carborane-fused cyclics. This method has the following features: (1) using o-carboranes instead of prefunctionalized iodocarboranes as starting materials; (2) employing earth abundant copper as a catalyst; and (3) room-temperature

  已经实现了光促进的，铜催化的邻氨基甲酸酯与芳基卤化物的笼型CH–H芳基化反应，从而轻松合成了各种1-芳基邻氨基甲酸酯和邻氨基甲烷稠合的环状物。该方法具有以下特点：（1）使用邻氨基甲酸酯代替预官能化的碘代氨基甲酸酯作为起始原料；（2）采用富土铜作为催化剂；（3）室温反应。对照实验表明该反应通过Cu催化的自由基偶联进行。
• Carborane–arene fused boracyclic analogues of polycyclic aromatic hydrocarbons accessed by intramolecular borylation
  作者：Yijie Li、Masilamani Tamizmani、Manjur O. Akram、Caleb D. Martin

  DOI：10.1039/d4sc00990h

  日期：——

  aromatics while dicarbadodecaborane clusters are branded as 3D aromatic molecules. In this work we prepare molecules that feature fused 2D/3D aromatic systems that represent boron-doped analogues of polycyclic aromatic hydrocarbons. The electron withdrawing nature of the ortho-carborane substituent enables swift arene borylation on boron bromide or hydride precursors to furnish five- and six-membered boracycles

  芳烃是 2D 芳族化合物，而二碳十二硼烷簇被称为 3D 芳族分子。在这项工作中，我们制备了具有稠合 2D/3D 芳香族系统的分子，这些芳香族系统代表多环芳烃的硼掺杂类似物。邻碳硼烷取代基的吸电子性质使得能够在溴化硼或氢化物前体上快速芳烃硼基化，以提供与芳烃共轭的五元和六元硼环。该机制通过 DFT 计算进行建模，暗示了协调的过渡态，并且分析光物理性质揭示了六元系统中的高量子产率。
• Palladium‐Catalyzed Direct B—H Oxygenation: Facile Synthesis of o‐Carboranofuranones†
  作者：Chenyang Guo、Zaozao Qiu、Zuowei Xie

  DOI：10.1002/cjoc.202400571

  日期：2024.12

  regioselectivities (B(3)-, B(4)-, and B(8,9)-selectivities). Herein, an efficient palladium-catalyzed direct cage B(4)–H oxygenation of o-carboranylacetic acids has been achieved, where the carboxylic group serves as not only a directing group, but also a coupling partner. A wide range of substituted o-carboranylacetic acids have been cyclized via the formation of B(4)−O bond to give the corresponding

  过渡金属催化的邻碳硼烷 B-H 活化的最新进展导致了笼式硼功能化的各种方法的快速发展。对于催化笼 B—H 酰氧基化，分子间氧合得到具有不同区域选择性 （B（3） - 、B（4） - 和 B（8,9） - 选择性的产物）。在此，已经实现了邻碳硼酰亚酸的高效钯催化直接笼 B（4）-H 氧合，其中羧基不仅作为定向基团，而且作为偶联伙伴。多种取代的邻碳硼乙酸已通过形成 B（4）−O 键进行环化，以中等至极高的产率得到相应的 γ-内酯。Pd（IV） 中间体被认为参与催化循环。这项工作为温和条件下 BH/OH 脱氢偶联反应生成碳硼烷特征功能分子提供了有价值的参考。