dichloro-5-trimethylsilylthien-2-ylborane | 1412912-67-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: dichloro-5-trimethylsilylthien-2-ylborane
• 英文别名: (5-Dichloroboranylthiophen-2-yl)-trimethylsilane；(5-dichloroboranylthiophen-2-yl)-trimethylsilane
• CAS: 1412912-67-4
• 化学式: C₇H₁₁BCl₂SSi
• 分子量: 237.033
• InChiKey: LCNHCIQSYIFUGR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.47
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  dichloro-5-trimethylsilylthien-2-ylborane 在 KC₈ 作用下， 以 甲苯 、 苯 为溶剂， 反应 2.66h， 生成 (CatB)(IMe){5-(Me3Si)C4H2S}B-B(H){5-(Me3Si)C4H2S}(IMe)
  参考文献：
  名称：

  BB债券的直接硼氢化：一个温和的策略B的扩散？B债券

  摘要：

  非经典结构的优先形成阻碍了对电子精确硼链的合成访问。现有的几种策略涉及强还原试剂或过渡金属催化剂，两者都有明显的缺点。的新的呋喃基和噻吩基取代diborenes合成被呈现，他们与儿茶酚硼烷（CatBH）直接硼氢化以形成新的电子精确乙沿着乙键以及B 3链。该反应是非对映选择性的，可在温和条件下进行，而无需使用通常在B-B偶联反应中使用的强还原剂或过渡金属催化剂。

  DOI：

  10.1002/anie.201309325
• 作为产物：
  描述：

  2,5-双(三甲基甲硅烷基)噻吩 在 三氯化硼 作用下， 以 neat (no solvent) 为溶剂， 反应 1.0h， 以87%的产率得到dichloro-5-trimethylsilylthien-2-ylborane
  参考文献：
  名称：

  1-Heteroaromatic-Substituted Tetraphenylboroles: π–π Interactions Between Aromatic and Antiaromatic Rings Through a B–C Bond

  摘要：

  A series of 2,3,4,5-tetraphenylboroles substituted with different aromatic heterocycles (thiophene, furan, pyrrole, and dithiophene) in the 1-position were synthesized and characterized by means of NMR, elemental analysis, and X-ray crystallography. In contrast to known 2,3,4,5-tetraphenylboroles, X-ray diffraction revealed a nearly coplanar arrangement of the aromatic heterocycles and the antiaromatic borole scaffold as a result of pi-conjugation, which could be substantiated by DFT calculations. Furthermore, the 2,2'-dithiophene-bridged bisborole (14) exhibits a large bathochromic shift in the absorption spectrum, demonstrating the exceptional Lewis acidity of the nonannulated borolyl moiety.

  DOI：

  10.1021/ja309935t

文献信息

• Increasing the Reactivity of Diborenes: Derivatization of NHC-Supported Dithienyldiborenes with Electron-Donor Groups
  作者：Dominic Auerhammer、Merle Arrowsmith、Philipp Bissinger、Holger Braunschweig、Theresa Dellermann、Thomas Kupfer、Carsten Lenczyk、Dipak K. Roy、Marius Schäfer、Christoph Schneider

  DOI：10.1002/chem.201704669

  日期：2018.1.2

  NHC‐supported 1,2‐dithienyldiborenes was synthesized from the corresponding (dihalo)thienylborane NHC precursors. NMR and UV/Vis spectroscopic data, as well as X‐ray crystallographic analyses, were used to assess the electronic and steric influences on the B=B double bond of various NHCs and electron‐donating substituents on the thienyl ligands. Crystallographic data showed that the degree of coplanarity of the

  从相应的（二卤代）噻吩基硼烷NHC前体合成了一系列NHC负载的1,2-二噻吩基二硼烷。NMR和UV / Vis光谱数据以及X射线晶体学分析被用于评估电子和空间位阻对各种NHC的B = B双键和噻吩基配体上给电子取代基的影响。晶体学数据表明，二硼烯核和噻吩基的共平面度高度依赖于取代基的空间。此外，取代基的供电子能力的任何增加都会导致HOMO的不稳定和所得二硼烷的更大不稳定性。
• Synthesis and Reduction of Sterically Encumbered Mesoionic Carbene-Stabilized Aryldihaloboranes
  作者：Merle Arrowsmith、Julian Böhnke、Holger Braunschweig、Haopeng Gao、Marc-André Légaré、Valerie Paprocki、Jens Seufert

  DOI：10.1002/chem.201700500

  日期：2017.9.7

  Sterically hindered, in situ generated 1,3,4-substituted 1,2,3-triazol-5-ylidene mesoionic carbenes (MICs) were employed to stabilize a number of aryl- and heteroaryldihaloboranes, as well as the first MIC-supported diborane. Reduction of borane adducts of the 1-(2,6-diisopropylphenyl)-3-methyl-4-tert-butyl-1,2,3-triazol-5-ylidene ligand with KC8 in non-coordinating solvents led to intramolecular C-H-

  受位阻的原位生成的1,3,4-取代的1,2,3-三唑-5-亚甲基中离子碳烯（MIC）用于稳定许多芳基和杂芳基二卤硼烷以及第一个MIC负载的乙硼烷。在非配位溶剂中用KC8还原1-（2,6-二异丙基苯基）-3-甲基-4-叔丁基-1,2,3-三唑-5-亚甲基的硼烷加合物导致分子内CH-并且，在支持配体的异丙基残基上进行CC活化。DFT计算表明，这些活化反应中的每一个均经由亚硼烷基中间体的不同异构体进行。
• Synthesis of the First Heteroaryl-Substituted Boryl Complexes: Strong Stabilizing Effects of Boron–Aryl π-Conjugation
  作者：Holger Braunschweig、Rian D. Dewhurst、Thomas Kramer

  DOI：10.1021/acs.inorgchem.5b00192

  日期：2015.4.6

  The first examples of heteroarylboryl complexes were prepared and have been found to be unreactive toward a range of strong reductants, strong Lewis bases, and halide-abstraction reagents. The inertness of the complexes is attributed to strong p-conjugation between the p-basic heteroaryl groups and the p-acidic boron atom. This hypothesis is supported by comparison of the structural and spectroscopic properties of the heteroarylboryl complexes with analogous previously reported homoarylboryl complexes, with the former showing greater coplanarity of the aryl ring with the boron atom and much less facile reactivity.
• Direct Hydroboration of BB Bonds: A Mild Strategy for the Proliferation of BB Bonds
  作者：Holger Braunschweig、Rian D. Dewhurst、Christian Hörl、Ashwini K. Phukan、Florian Pinzner、Stefan Ullrich

  DOI：10.1002/anie.201309325

  日期：2014.3.17

  strongly reducing reagents or transition‐metal catalysts, both with distinct disadvantages. The synthesis of new furyl‐ and thienyl‐substituted diborenes is presented, along with their direct hydroboration with catecholborane (CatBH) to form a new electron‐precise BB bond and a B3 chain. The reaction is diastereoselective and proceeds under mild conditions without the use of strong reducing agents or transition‐metal

  非经典结构的优先形成阻碍了对电子精确硼链的合成访问。现有的几种策略涉及强还原试剂或过渡金属催化剂，两者都有明显的缺点。的新的呋喃基和噻吩基取代diborenes合成被呈现，他们与儿茶酚硼烷（CatBH）直接硼氢化以形成新的电子精确乙沿着乙键以及B 3链。该反应是非对映选择性的，可在温和条件下进行，而无需使用通常在B-B偶联反应中使用的强还原剂或过渡金属催化剂。
• 1-Heteroaromatic-Substituted Tetraphenylboroles: π–π Interactions Between Aromatic and Antiaromatic Rings Through a B–C Bond
  作者：Holger Braunschweig、Alexander Damme、J. Oscar C. Jimenez-Halla、Christian Hörl、Ivo Krummenacher、Thomas Kupfer、Lisa Mailänder、Krzysztof Radacki

  DOI：10.1021/ja309935t

  日期：2012.12.12

  A series of 2,3,4,5-tetraphenylboroles substituted with different aromatic heterocycles (thiophene, furan, pyrrole, and dithiophene) in the 1-position were synthesized and characterized by means of NMR, elemental analysis, and X-ray crystallography. In contrast to known 2,3,4,5-tetraphenylboroles, X-ray diffraction revealed a nearly coplanar arrangement of the aromatic heterocycles and the antiaromatic borole scaffold as a result of pi-conjugation, which could be substantiated by DFT calculations. Furthermore, the 2,2'-dithiophene-bridged bisborole (14) exhibits a large bathochromic shift in the absorption spectrum, demonstrating the exceptional Lewis acidity of the nonannulated borolyl moiety.