o-(dimesitylboryl)(dimethylsilyl)benzene | 936499-83-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: o-(dimesitylboryl)(dimethylsilyl)benzene
• 英文别名: o-[(dimesitylboryl)phenyl]dimethylsilane；[2-Bis(2,4,6-trimethylphenyl)boranylphenyl]-dimethylsilane；[2-bis(2,4,6-trimethylphenyl)boranylphenyl]-dimethylsilane
• CAS: 936499-83-1
• 化学式: C₂₆H₃₃BSi
• 分子量: 384.445
• InChiKey: UHGUAAOACIFPPK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.75
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  o-(dimesitylboryl)(dimethylsilyl)benzene 、 水 以 四氢呋喃 为溶剂， 以90%的产率得到o-(hydroxydimethylsilyl)(dimesitylboryl)benzene
  参考文献：
  名称：

  Intramolecular Reaction of Silanol and Triarylborane: Boron−Aryl Bond Cleavage and Formation of a Si−O−B Heterocyle

  摘要：

  o-(Hydroxydimethylsilyl)(dimesitylboryl)benzene (1) underwent intrarnolecular cyclization to give 5,5-dimesityl-2,2-dimethyl-3,4-benzo-1,2,5-oxasilaboracyclopentene (4) and mesitylene by boron-aryl bond cleavage. Whereas triethylamine as an additive accelerated the cyclization, DBU stabilized a silyloxyborate complex, 1,8-diazabicyclo[5.4.0]-7-undecenium 5,5-dimesityl-2,2-dimethyl-3,4-benzo-1,2,5-oxasilaboratacyclopentene, which was characterized by X-ray crystallographic analysis and HF calculations. The deuterium-labeling experiments revealed that the hydrogen migrated from the hydroxyl group in 1 to the leaving mesitylene.

  DOI：

  10.1021/om8004405
• 作为产物：
  描述：

  二(三甲苯基)氟化硼 、 (o-溴苯基)(二甲基)硅烷 在 叔丁基锂 作用下， 以 乙醚 、 正戊烷 为溶剂， 反应 22.0h， 以81%的产率得到o-(dimesitylboryl)(dimethylsilyl)benzene
  参考文献：
  名称：

  Dehydrogenative Condensation of (o-Borylphenyl)hydrosilane with Alcohols and Amines

  摘要：

  邻[(二甲基苄基)苯基]二甲基硅烷（1a）与醇和胺发生脱氢缩合反应，生成相应的烷氧基硅烷 4-7 和氨基硅烷 8 和 9，产率从中等到较高不等。1a 中的正硼基能亲电激活 Si-H 键。

  DOI：

  10.1246/cl.2007.362

文献信息

• Intramolecular HAr Ligand Exchange between Silicon and Boron: Functionality Transfer of SiH to BH
  作者：Atsushi Kawachi、Hiroshi Morisaki、Norimasa Nishioka、Yohsuke Yamamoto

  DOI：10.1002/asia.201100678

  日期：2012.3.5

  o‐C6H4(SiR3−nHn)(BMes2) (1; R=Me, Ph; n=1, 2) undergo MesH (Mes=mesityl) ligand exchange between the silicon atom and the boron atom to form o‐C6H4(SiMesR3−nHn−1)(BMesH) (6) upon heating. The resulting hydroborane intermediates (6) immediately react with benzaldehyde to afford their corresponding benzyloxyboranes (5). A DFT study of model compounds reveals the transition states of the ligand exchange

  ø -C 6 ħ 4（SIR 3 - ñ ħ Ñ）（BMES 2）（1 ; R = Me中的Ph值; Ñ = 1，2）经历的Mes  H（的Mes =异亚丙基丙酮）中的硅原子和配位体之间交换硼原子在加热时形成o ‐ C 6 H 4（SiMesR 3 − n H n − 1）（BMesH）（6）。生成的氢硼烷中间体（6）立即与苯甲醛反应，得到其相应的苄氧基硼烷（5）。DFT对模型化合物的研究揭示了配体交换的过渡态。硼中心从硅原子中提取氢化物是达到过渡态的关键，其中包括三配位的甲硅烷基阳离子部分和四配位的硼氢化物部分。
• Reaction of o-(HSiR2)(BMes2)C6H4 with a fluoride ion: Fluoride attack at silicon and hydride transfer from silicon to boron to form FSi⋅⋅⋅HB interaction
  作者：Atsushi Kawachi、Hiroshi Morisaki、Atsushi Tani、Masatoshi Zaima、Yohsuke Yamamoto

  DOI：10.1002/hc.20709

  日期：——

  Reactions of o-(HSiR2)(BMes2)C6H4 (R = Me (3a), Ph (3b)) with a fluoride ion afford [o-(FSiR2)(HBMes2)C6H4]− (R = Me (5a), Ph (5b)), which involve the FSi⋅⋅⋅HB interaction to render the silicon atom pentacoordinate. The FSi⋅⋅⋅HB interaction in 5a was confirmed by X-ray crystallographic analysis and “atoms-in-molecules” (AIM) analysis. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:471–475, 2011;

  o-(HSiR2)(BMes2)C6H4 (R = Me (3a), Ph (3b)) 与氟离子反应得到 [o-(FSiR2)(HBMes2)C6H4]− (R = Me (5a), Ph (5b))，其中涉及 FSi⋅⋅⋅HB 相互作用以呈现硅原子五坐标。X 射线晶体学分析和“分子中原子”（AIM）分析证实了 5a 中的 FSi⋅⋅⋅HB 相互作用。© 2011 Wiley Periodicals, Inc. 杂原子化学 22:471–475, 2011; 在 wileyonlinelibrary.com 上在线查看这篇文章。DOI 10.1002/hc.20709
• Intramolecular Reaction of Silanol and Triarylborane: Boron−Aryl Bond Cleavage and Formation of a Si−O−B Heterocyle
  作者：Atsushi Kawachi、Masatoshi Zaima、Yohsuke Yamamoto

  DOI：10.1021/om8004405

  日期：2008.9.22

  o-(Hydroxydimethylsilyl)(dimesitylboryl)benzene (1) underwent intrarnolecular cyclization to give 5,5-dimesityl-2,2-dimethyl-3,4-benzo-1,2,5-oxasilaboracyclopentene (4) and mesitylene by boron-aryl bond cleavage. Whereas triethylamine as an additive accelerated the cyclization, DBU stabilized a silyloxyborate complex, 1,8-diazabicyclo[5.4.0]-7-undecenium 5,5-dimesityl-2,2-dimethyl-3,4-benzo-1,2,5-oxasilaboratacyclopentene, which was characterized by X-ray crystallographic analysis and HF calculations. The deuterium-labeling experiments revealed that the hydrogen migrated from the hydroxyl group in 1 to the leaving mesitylene.
• Dehydrogenative Condensation of (<i>o</i>-Borylphenyl)hydrosilane with Alcohols and Amines
  作者：Atsushi Kawachi、Masatoshi Zaima、Atsushi Tani、Yohsuke Yamamoto

  DOI：10.1246/cl.2007.362

  日期：2007.3.5

  o-[(Dimesitylboryl)phenyl]dimethylsilane (1a) undergoes dehydrogenative condensation with alcohols and amines, giving the corresponding alkoxysilanes 4–7 and aminosilanes 8 and 9 in moderate to high yields. It is plausible that the ortho-boryl group in 1a electrophilically activates the Si–H bond.

  邻[(二甲基苄基)苯基]二甲基硅烷（1a）与醇和胺发生脱氢缩合反应，生成相应的烷氧基硅烷 4-7 和氨基硅烷 8 和 9，产率从中等到较高不等。1a 中的正硼基能亲电激活 Si-H 键。