1-(thien-2-yl)-2,3,4,5-tetraphenylborole | 1412912-68-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1-(thien-2-yl)-2,3,4,5-tetraphenylborole
• 英文别名: 2,3,4,5-tetraphenyl-1-(thiophene-2-yl)-borole；1-(2-thienyl)-2,3,4,5-tetraphenylborole；1-thienyl-2,3,4,5-tetraphenylborole；2-(2,3,4,5-Tetraphenylborol-1-yl)thiophene；2-(2,3,4,5-tetraphenylborol-1-yl)thiophene
• CAS: 1412912-68-5
• 化学式: C₃₂H₂₃BS
• 分子量: 450.412
• InChiKey: HYDDSPONRMTONL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.76
• 重原子数：
  34
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  1-(thien-2-yl)-2,3,4,5-tetraphenylborole 以 甲苯 、 苯 为溶剂， 反应 76.0h， 生成
  参考文献：
  名称：

  重新思考硼酸环加成反应性

  摘要：

  Boroles 因其在合成、小分子活化和功能材料方面的无数应用而引起了广泛的兴趣。它们的性质和反应性与环状共轭二烯系统密切相关，该系统已被证明参与环加成反应，例如与炔烃的 Diels-Alder 反应。从文献中判断，由硼与炔烃的热反应产生硼降冰片二烯、硼烷和三环硼环己烯的反应步骤似乎很好理解。在这里，我们通过证明七元钻孔（即，七苯基硼烷和两种在硼上被噻吩基和氯取代基取代的衍生物）与相应的双环硼降冰片二烯（Diels-Alder 直接产物）处于动态平衡状态，但不是从反应中分离出来的产物。加热逐渐将异构体混合物转化为荧光三环硼环己烯，这是该系列中最稳定的异构体。机械 DFT 计算的结果表明，三环化合物源自硼降冰片二烯而不是硼烷，此前人们认为后者是纯环过程中的中间体。

  DOI：

  10.1002/chem.202101290
• 作为产物：
  描述：

  dichlorothiophene-2-ylborane 、 1,1-dimethyl-2,3,4,5-tetraphenylstannole 以 二氯甲烷 为溶剂， 反应 3.0h， 以70%的产率得到1-(thien-2-yl)-2,3,4,5-tetraphenylborole
  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

• Adducts of the Parent Boraphosphaketene H ₂ BPCO and their Decarbonylative Insertion Chemistry
  作者：Stephan Hagspiel、Felipe Fantuzzi、Rian D. Dewhurst、Annalena Gärtner、Felix Lindl、Anna Lamprecht、Holger Braunschweig

  DOI：10.1002/anie.202103521

  日期：2021.6.7

  cyclodimers are prepared. One of these adducts is shown to undergo mild decarbonylation and phosphinidene insertion into a B−C bond of a borole, forming very rare examples of 1,2-phosphaborinines, B/P isosteres of benzene. The strong donor properties of these 1,2-phosphaborinines are confirmed by the synthesis of their π complexes with the Group 6 metals.

  制备了母体硼磷烯酮(H 2 B-PCO)及其环二聚体的路易斯碱加合物的第一个实例。其中一种加合物会发生温和的脱羰作用，并将膦亚膦插入硼杂环戊烯的 B−C 键中，形成非常罕见的 1,2-磷硼啉（苯的 B/P 电子等排体）。这些 1,2-磷硼烷的强供体特性通过其与第 6 族金属的 π 配合物的合成得到证实。
• Scope of the Thermal Ring-Expansion Reaction of Boroles with Organoazides
  作者：Holger Braunschweig、Mehmet Ali Celik、Theresa Dellermann、Gernot Frenking、Kai Hammond、Florian Hupp、Hauke Kelch、Ivo Krummenacher、Felix Lindl、Lisa Mailänder、Jonas H. Müssig、Annika Ruppert

  DOI：10.1002/chem.201700749

  日期：2017.6.12

  steric factors have been investigated in the thermal ring expansion of boroles with organic azides, a reaction that provides access to highly arylated 1,2-azaborinines, BN analogues of benzene. Reactions of a variety of boroles and organic azides demonstrate that the synthetic method is quite general in furnishing 1,2-azaborinines, but the respective reaction rates reveal a strong dependence on the substituents

  在有机化合物叠氮化物的热扩环中，已经研究了电子和位阻因素，该反应可提供高度芳基化的1,2-氮杂嘌呤胺（苯的BN类似物）。各种硼酸酯和有机叠氮化物的反应表明，合成方法在提供1,2-氮杂嘌呤胺类化合物方面非常普遍，但各自的反应速率显示出对两种反应物上取代基的强烈依赖性。该产品已通过UV / Vis，电化学，NMR和X射线衍射方法进行了表征，阐明了它们的组成并突出了取代基对1,2-氮杂鸟嘌呤电子结构的影响。此外，通过DFT研究，分析了1,2-氮杂鸟嘌呤形成的几种可能的机理途径，
• Borabicyclo[3.2.0]heptadiene: A Fused Bicyclic Isomer of Borepin
  作者：Hauke Kelch、Stephanie Kachel、Johannes Wahler、Mehmet Ali Celik、Andreas Stoy、Ivo Krummenacher、Thomas Kramer、Krzysztof Radacki、Holger Braunschweig

  DOI：10.1002/chem.201803509

  日期：2018.10.12

  A new isomer of borepin, identified as 2‐borabicyclo[3.2.0]hepta‐3,6‐diene by single‐crystal X‐ray diffraction and heteronuclear NMR spectroscopy, was obtained by reaction of 1‐mesityl‐2,3,4,5‐tetraphenylborole with the diaminoalkyne bis(piperidyl)acetylene. Analogous reactions of the alkyne with other borole derivatives generated seven‐membered borepins, in which a second equivalent of the alkyne

  通过单晶X-射线衍射和异核NMR光谱鉴定了一种新型的硼销异构体，称为2-borabicyclo [3.2.0] hepta-3,6-二烯，是通过1-mesityl-2,3,4反应制得的，5-四苯基硼烷与二氨基炔烃双（哌啶基）乙炔。炔烃与其他硼衍生物的类似反应产生了七元硼酸酯，其中发现第二个等价的炔烃插入环外BC键中。讨论了机械DFT研究的结果以及硼烷对二氨基炔烃的反应性差异。
• Rethinking Borole Cycloaddition Reactivity
  作者：Felix Lindl、Xueying Guo、Ivo Krummenacher、Florian Rauch、Anna Rempel、Valerie Paprocki、Theresa Dellermann、Tom E. Stennett、Anna Lamprecht、Tobias Brückner、Krzysztof Radacki、Guillaume Bélanger‐Chabot、Todd B. Marder、Zhenyang Lin、Holger Braunschweig

  DOI：10.1002/chem.202101290

  日期：2021.8.2

  the cyclic conjugated diene system, which has been shown to participate in cycloaddition reactions, such as the Diels-Alder reaction with alkynes. The reaction steps leading to boranorbornadienes, borepins and tricyclic boracyclohexenes from the thermal reaction of boroles with alkynes are seemingly well understood as judged from the literature. Herein, we question the long-established mechanistic picture

  Boroles 因其在合成、小分子活化和功能材料方面的无数应用而引起了广泛的兴趣。它们的性质和反应性与环状共轭二烯系统密切相关，该系统已被证明参与环加成反应，例如与炔烃的 Diels-Alder 反应。从文献中判断，由硼与炔烃的热反应产生硼降冰片二烯、硼烷和三环硼环己烯的反应步骤似乎很好理解。在这里，我们通过证明七元钻孔（即，七苯基硼烷和两种在硼上被噻吩基和氯取代基取代的衍生物）与相应的双环硼降冰片二烯（Diels-Alder 直接产物）处于动态平衡状态，但不是从反应中分离出来的产物。加热逐渐将异构体混合物转化为荧光三环硼环己烯，这是该系列中最稳定的异构体。机械 DFT 计算的结果表明，三环化合物源自硼降冰片二烯而不是硼烷，此前人们认为后者是纯环过程中的中间体。
• 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.