2-methyl-1-phenyl-1,2-dicarba-closo-dodecaborane(12) | 17806-86-9

• 英文名称: 2-methyl-1-phenyl-1,2-dicarba-closo-dodecaborane(12)
• 英文别名: 1-methyl-2-phenyl-o-carborane；1-Ph-2-Me-1,2-closo-C2B10H10；1-phenyl-2-methyl-o-caborane；closo-1-Ph-2-Me-1,2-C2B10H10
• CAS: 17806-86-9
• 化学式: C₉H₁₈B₁₀
• 分子量: 234.352
• InChiKey: WRPFYEXDQXSJKB-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：

  2-methyl-1-phenyl-1,2-dicarba-closo-dodecaborane(12) 、 thallium(I) acetate 在 KOH 作用下， 以 乙醇 、 水 为溶剂， 以27.4%的产率得到Tl2[7-Ph-8-Me-7,8-nido-C2B9H9]
  参考文献：
  名称：

  Enhanced slip distortions in 1-phenyl-2-methyldicarbaplatinaboranes. Conformational destabilisation in the isomerisation of 1-phenyldicarbaplatinaboranes

  摘要：

  The compounds Tl-2[7-Ph-8-Me-7,8-nido-C2B9H9], [C5H10NH2] [7-Ph-8-Me-7,8-nido-C2B9H10], 1-Ph-2-Me-3,3-L(2)-3,1,2-PtC2B9H9 [L = PMe(2)Ph, PEt(3), PPh(3) or P(C(6)H(4)Me-p)(3)] have been prepared and characterised. The platinum complexes were obtained from the reactions between Tl-2[7-Ph-8-Me-7,8-nido-C2B9H9] and the appropriate [PtCl2(PR(3))(2)] species. Crystallographic studies upon the compounds where L = PEt(3) and two crystalline modifications of that where L = PPh(3) afforded evidence of a substantial influence of intramolecular crowding upon the observed structures, so that the lateral slippage (Delta) of the metal fragment is significantly enhanced: Delta = 0.74 and 0.94 and 0.91 Angstrom respectively. These compounds do not isomerise under conditions which produce rearrangement in the corresponding (less-congested) derivatives of 1-phenylcarbaborane, consistent with the proposed conformational destabilisation in the latter system.

  DOI：

  10.1039/dt9950001755
• 作为产物：
  描述：

  1-I-2-CH3-o-CB10H10C 、 苯 在 sodium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以86%的产率得到2-methyl-1-phenyl-1,2-dicarba-closo-dodecaborane(12)
  参考文献：
  名称：

  碘碳硼烷与未活化的（杂）芳烃的光芳基化：1,2-[（（杂）芳基] n-o-碳硼烷（n = 1,2）和邻-碳硼烷融合的环的轻松合成

  摘要：

  首次实现了在室温下用未活化的芳烃/杂芳烃将碘代碳硼烷进行光芳基化，从而导致了多种笼型碳单（杂）芳基化和二（杂）芳基化的邻碳硼烷的简便合成。这项工作代表了一种清洁，高效，无过渡金属且廉价的官能化碳硼烷合成方法，与已知方法相比，该方法具有明显的优势。

  DOI：

  10.1002/anie.201610810

文献信息

• Nickel-Catalyzed Cross-Coupling Reactions of<i>o</i>-Carboranyl with Aryl Iodides: Facile Synthesis of 1-Aryl-<i>o</i>-Carboranes and 1,2-Diaryl-<i>o</i>-Carboranes
  作者：Cen Tang、Zuowei Xie

  DOI：10.1002/anie.201502502

  日期：2015.6.22

  A nickel‐catalyzed arylation at the carbon center of o‐carborane cages has been developed, thus leading to the preparation of a series of 1‐aryl‐o‐carboranes and 1,2‐diaryl‐o‐carboranes in high yields upon isolation. This method represents the first example of transition metal catalyzed C,C′‐diarylation by cross‐coupling reactions of o‐carboranyl with aryl iodides.

  已经开发了在邻-甲硼烷笼碳中心的镍催化的芳基化反应，从而导致在分离后以高收率制备了一系列的1-芳基-邻-碳戊烷和1,2-二芳基-邻碳烷。该方法是过渡金属催化邻氨基甲酰基与芳基碘化物交叉偶联反应的C，C'-二芳基化的第一个实例。
• Palladium-Catalyzed Selective Mono-/Tetraacetoxylation of <i>o</i>-Carboranes with Acetic Acid via Cross Dehydrogenative Coupling of Cage B–H/O–H Bonds
  作者：Tao-Tao Xu、Ke Cao、Ji Wu、Cai-Yan Zhang、Junxiao Yang

  DOI：10.1021/acs.inorgchem.8b00038

  日期：2018.3.5

  with acetic acid via cross dehydrogenative coupling of cage B–H/O–H bonds has been developed, and a series of mono- and tetraacetoxylated o-carboranes have been synthesized with moderate to good yields as well as good selectivity. Mechanistic studies indicate that the acetoxyl originates from acetic acid directly, and a nucleophilic addition of PdIV-oxo species and dehydration process is proposed.

  通过笼型B–H / O–H键的交叉脱氢偶联，选择性合成了邻氨基甲酸酯与乙酸的单/四乙酰氧基化反应，并且合成了一系列中等至良好收率的单-和四乙酰氧基化的邻氨基甲酸酯。以及良好的选择性。机理研究表明，乙酰氧基直接来源于乙酸，并提出了亲核加成Pd IV-氧代物种和脱水过程。
• Practical Synthesis of B(9)-Halogenated Carboranes with <i>N</i>-Haloamides in Hexafluoroisopropanol
  作者：Wenjing Guo、Chenyang Guo、Yan-Na Ma、Xuenian Chen

  DOI：10.1021/acs.inorgchem.2c00074

  日期：2022.4.4

  The B(9)-H halogenation of o-carborane and m-carborane was achieved with excellent selectivities in hexafluoroisopropanol (HFIP) under simple reaction conditions: single reagent [trichloroisocyanuric acid (TCCA), tribromoisocyanuric acid (TBCA) or N-iodosuccinimide (NIS)], catalyst-free, air-/moisture-tolerant, and convenient work-up. With this method, a variety of 9-halogenated o-carboranes and m-carboranes

  在简单的反应条件下，在六氟异丙醇 (HFIP) 中以优异的选择性实现邻碳硼烷和间碳硼烷的 B(9)-H 卤化：单一试剂 [三氯异氰脲酸 (TCCA)、三溴异氰脲酸 (TBCA) 或N-碘代琥珀酰亚胺 ( NIS)]，无催化剂，耐空气/耐湿，后处理方便。采用这种方法，得到了多种 9-卤代邻碳硼烷和间碳硼烷，其产率从良好到优异，具有广泛的官能团耐受性。
• 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。
• Palladium catalyzed/silver tuned selective mono-/tetra-acetoxylation of o-carboranes via B–H activation
  作者：Ke Cao、Tao-Tao Xu、Ji Wu、Linhai Jiang、Junxiao Yang

  DOI：10.1039/c6cc06200h

  日期：——

  Silver tuned the selective mono-/tetra-acetoxylation of o-carboranes via palladium catalyzed B–H activation.

  Silver通过钯催化的B-H活化实现了对o-碳硼烷的选择性单/四乙酰氧化。