3-iodo-o-carborane | 137495-63-7

• 英文名称: 3-iodo-o-carborane
• 英文别名: 3-iodo-1,2-dicarba-closo-dodecaborane；3-iodo-ortho-carborane；3-I-o-carborane；3-I-1,2-closo-C2B10H11；3-I-1,2-closo-C2B11H
• CAS: 137495-63-7
• 化学式: C₂H₁₁B₁₀I
• 分子量: 270.124
• InChiKey: GCTKOZGVBKYSCQ-UHFFFAOYSA-N

计算性质

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

反应信息

• 作为反应物：
  描述：

  3-iodo-o-carborane 在 三苯基膦 、 锌 作用下， 以 吡啶 为溶剂， 生成 1,2-dicarba-closo-dodecaborane(12)
  参考文献：
  名称：

  The BI activation in o-carborane clusters: their fate towards BH. Easy synthesis of [7,10-C2B10H13]−

  摘要：

  The reaction of 3-I-o-carborane with Cu, Cu/PPh3 [Ni(PPh3)(3)], or [Pd(PPh3)(4)] has been Studied to find the suitability of B-iodine substituted carboranes as sources of new boron-derivatives. In all these reactions a hydrodehalogenation reaction to yield o-carborane has been produced, indicating that B-I activation takes place. It may be considered that B-I adds oxidatively to M, but alternative explanations can be given. Reaction of 3-I-o-carborane with Na/naphthalene also produced o-carborane showing that albeit an oxidative addition is impossible for sodium the same hydrodehalogenation had taken place. The same result was also formed with Mg. Addition of 1,2-dibromoethane to the Mg/o-carborane reaction yielded [7,10-C2B10-H-13](-). Then, the sequence 3-I-o-carborane --> o-carborane [7,10-C2B10H13](-) can be generated with only reducing agents. The synthetic procedure for [7,10-C2B10H13](-) is very simple and produces a 97% yield of [NMe4][7,10-C2B10H13]. Basically, 1,2-C2B10H12 and Mg in excess are refluxed in THF in the presence of I-2 and 1,2-dibromoethane. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)01108-1
• 作为产物：
  描述：

  Li2{nido-7,8-C2B9H11} 、 三碘化硼 以 正己烷 为溶剂， 反应 18.0h， 以42%的产率得到3-iodo-o-carborane
  参考文献：
  名称：

  可见光促进的镍催化碘碳硼烷与（杂）芳烃通过硼中心碳硼烷基自由基的交叉偶联

  摘要：

  通过可见光促进的碘原子提取，首次开发了在 B(3)、B(4) 和 B(9) 位置生成高价硼中心碳硼烷基自由基的一般策略。○-碳硼烷通过低价镍络合物。这些自由基与各​​种（杂）芳烃反应，在室温下以非常好的至极好的产率和广泛的底物范围提供范围广泛的笼式 B-芳基化碳硼烷衍生物。它们的亲电性取决于笼的顶点电荷并遵循 B(3) > B(4) > B(9) 的顺序。可见光和镍催化剂都被证明对硼中心碳硼烷基自由基的产生至关重要。对照实验支持硼自由基的参与。还提出了与这些反应相关的反应机理。该策略为在选定的硼顶点处生成以硼为中心的碳硼烷基自由基提供了一种新的方案，从而可以轻松合成一大类笼形硼取代的碳硼烷分子。

  DOI：

  10.1021/jacs.2c02329

文献信息

• Synthesis, characterization, and preliminary fluorescence study of a mixed-ligand bis(dicarbollyl)nickel complex bearing a tryptophan-BODIPY FRET couple
  作者：Natalia I. Shlyakhtina、Alexander V. Safronov、Yulia V. Sevryugina、Satish S. Jalisatgi、M. Frederick Hawthorne

  DOI：10.1016/j.jorganchem.2015.04.035

  日期：2015.12

  In continuation of our work on nickelacarborane-based nanomolecular devices, the design and synthesis of a bis(dicarbollyl)nickel complex, in both formal Ni(III) and Ni(IV) oxidation states, bearing two fluorophore molecules capable of fluorescence resonance energy transfer (FRET) was performed. The FRET couple with a small Förster radius (R0 of 26Å) consisted of tryptophan and 4,4-difluoro-4-bora-3a

  在我们继续进行基于镍碳硼烷的纳米分子装置的工作时，设计和合成了处于正式Ni（III）和Ni（IV）氧化态的双（二甲碳烯基）镍配合物，其带有两个能够进行荧光共振能量转移的荧光团分子（FRET）被执行。FRET夫妇具有较小的Förster半径（R 0为26Å），由色氨酸和4,4-二氟-4-硼3a，4a-二氮杂-s-茚并二烯（BODIPY）组成。每个荧光团通过包含两对交替的乙炔基和对亚苯基的刚性接头连接到镍碳硼烷核上，这取决于镍碳硼烷核的构型在荧光团分子之间产生特定的距离（l）。存在（13Å< l在设计的系统中<39Å）或没有（l >39Å）的能量转移，可以洞悉溶液中镍碳硼烷的构象变化。经由多步有机/有机金属合成来制备目标镍碳硼烷。中间体和最终产物的结构和组成是通过光谱法和X射线结构分析相结合来确定的。进行了制备的镍金属碳硼烷的初步荧光研究。
• Pd‐Catalyzed Selective Bifunctionalization of 3‐Iodo‐ <i>o</i> ‐Carborane by Pd Migration
  作者：Yixiu Ge、Jie Zhang、Zaozao Qiu、Zuowei Xie

  DOI：10.1002/anie.201914500

  日期：2020.3.16

  A palladium-catalyzed highly selective 3,4-bifunctionalization of 3-I-o-carborane has been developed, leading to the preparation of 3-alkenyl-4-R-o-carboranes (R=alkyl, alkynyl, aryl, allyl, CN, and amido) in high to excellent yields. This protocol combines the sequential activation of cage B(3)-I and B(4)-H bonds by Pd migration from exo-alkenyl sp2 C to cage B(4), which is driven by thermodynamic

  已经开发了钯催化的3-Io-碳烷的高选择性3,4-双官能化，从而制备了3-烯基-4-Ro-碳烷（R =烷基，炔基，芳基，烯丙基，CN和酰胺基） ）以高至优异的产量。该协议通过从外链烯基sp2 C到热力学力驱动的B（4）的Pd迁移结合了笼状B（3）-I和B（4）-H键的顺序激活。这代表了具有两个不同取代基的碳硼烷选择性双官能化的全新策略。
• New Approach to the Synthesis of 3-Alkyl-1,2-dicarba-<i>closo</i>-dodecaboranes: Reaction of Alkyldichloroboranes with Thallium Dicarbollide
  作者：Alexander V. Safronov、Natalia I. Shlyakhtina、M. Frederick Hawthorne

  DOI：10.1021/om201060e

  日期：2012.4.9

  2-dicarba-closo-dodecaboranes were prepared in good yields via the reaction of alkyldichloroboranes, which were generated in situ through hydroboration of the corresponding alkenes with a dichloroborane–dioxane complex, with thallium dicarbollides in anhydrous dichloromethane at room temperature. This reaction also affords insertion products with new thallium dicarbollides prepared from 3-iodo- and 9-iodo-1,2-dic

  许多3-烷基取代的1,2- dicarba-闭合碳-dodecaboranes经由alkyldichloroboranes的反应，其产生了良好的收率制备原位与通过相应的烯烃的硼氢化一个二氯硼二恶烷络合物，铊dicarbollides在室温下用无水二氯甲烷洗脱。该反应还得到插入产品具有新铊dicarbollides从3-碘和9-碘代-1,2- dicarba-制备闭合碳-dodecaboranes。将合成的3-烷基-1,2- dicarba-闭合碳-dodecaboranes可以在B（6）原子被选择性地脱硼，以形成阴离子的3-烷基-7,8- dicarba-巢-undecaborates。所有化合物均通过NMR和MS技术表征。
• Pd-Catalyzed sequential B(3)–I/B(4)–H bond activation for the synthesis of 3,4-benzo-<i>o</i>-carboranes
  作者：Yixiu Ge、Jie Zhang、Zaozao Qiu、Zuowei Xie

  DOI：10.1039/d0dt03740k

  日期：——

  A palladium-catalyzed sequential B(3)–I and B(4)–H bond activation has been achieved for the synthesis of 3,4-benzo-o-carboranes via a formal [2 + 2 + 2] cycloaddition of 3-I-o-carborane with 2 equiv. of arylalkynes. This represents a new protocol to construct o-carborane-fused cyclics in one process, in which the Pd fragment migrates formally from the B(3) to B(4) position of the cage.

  钯催化的顺序B（3）-I和B（4）-H键活化已经实现为3,4-苯并合成Ô -carboranes通过正式的[2 + 2 + 2]的3-环加成2当量的I- o-碳硼烷。芳炔。这代表了在一个过程中构建邻-碳环稠合环的新方案，其中Pd片段从笼的B（3）位置正式迁移到B（4）位置。
• Example of an intramolecular, non-classical C–H⋯π hydrogen bonding interaction in an Arylcarborane derivative
  作者：Bhaskar M. Ramachandran、Carolyn B. Knobler、M. Frederick Hawthorne

  DOI：10.1016/j.molstruc.2005.10.006

  日期：2006.3

  Abstract The synthesis and X-ray diffraction study of 3-(2-biphenyl)-1,2- C2B10H11, 1, provides an example of an intramolecular non-classical C–H⋯π hydrogen bonding interaction in which the same aromatic π-electron-donating group which interacts with the carborane C–H is also connected to the carborane cage.

  摘要 3-(2-联苯)-1,2- C2B10H11, 1 的合成和 X 射线衍射研究提供了一个分子内非经典 C–H⋯π 氢键相互作用的例子，其中相同的芳香族 π-与碳硼烷 C-H 相互作用的给电子基团也连接到碳硼烷笼。