1,2-bis(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzene | 1239569-25-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,2-bis(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzene
• 英文别名: 2-[2-(5,5-Dimethyl-1,3,2-dioxaborinan-2-yl)phenyl]-5,5-dimethyl-1,3,2-dioxaborinane
• CAS: 1239569-25-5
• 化学式: C₁₆H₂₄B₂O₄
• 分子量: 301.986
• InChiKey: UNFLJUOGCSVTFX-UHFFFAOYSA-N

物化性质

• 熔点：
  55-58 °C
• 沸点：
  437.9±28.0 °C(predicted)
• 密度：
  1.05±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.22
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  neopentylglycolborane 、 邻二氯苯 在 1,1'-双(二苯基膦)二茂铁 、 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) 、 三乙胺 、 锌 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以76%的产率得到1,2-bis(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzene
  参考文献：
  名称：

  Zero-Valent Metals Accelerate the Neopentylglycolborylation of Aryl Halides Catalyzed by NiCl₂-Based Mixed-Ligand Systems

  摘要：

  The highly active mixed-ligand catalytic system NiCl2(dppp)/dppf combined with the reducing effect of zerovalent Zn and of other metals was used to demonstrate a method for the dramatic acceleration of the rate and for the enhancement of the yield of Ni-catalyzed neopentylglycolborylation of aryl halides A diversity of electron-rich and electron-deficient aryl iodides, bromides, and chlorides were efficiently neopentylglycolborylated, typically in 1 h or less This acceleration is particularly remarkable for the generally less reactive aryl bromides and chlorides and for all ortho-substituted aryl halides By accelerating the rate of borylation and reducing its reaction time to complete conversion, pathways leading to protodeborylated or hydrodehalogenated side products have a reduced impact on the outcome of the overall reaction Although Zn powder was the reducing agent of choice, compatibility of this technique with more readily recoverable Zn chips, as well as other metals such as Mn, Mg, Fe, Al, and Ca, has demonstrated the broad scope of this synthetic method

  DOI：

  10.1021/jo101718v

文献信息

• Neopentylglycolborylation of <i>ortho</i>-Substituted Aryl Halides Catalyzed by NiCl₂-Based Mixed-Ligand Systems
  作者：Costel Moldoveanu、Daniela A. Wilson、Christopher J. Wilson、Pawaret Leowanawat、Ana-Maria Resmerita、Chi Liu、Brad M. Rosen、Virgil Percec

  DOI：10.1021/jo101023t

  日期：2010.8.20

  NiCl2-based mixed-ligand systems were shown to be very effective catalysts for the neopentylglycolborylation of aryl iodides, bromides, and chlorides bearing electron-rich and electron-deficient ortho-substituents. Although NiCl2-based single-ligand catalytic systems were able to mediate neopentylglycolborylation of selected substrates, they were not as effective for all substrates, highlighting the value of the mixed-ligand concept. Optimization of the Ni(II)-catalyzed neopentylglycolborylation of 2-iodoanisole and methyl 2-iodobenzoate demonstrated that, while the role of ligand and coligand in the conversion of Ni(II) precatalyst to Ni(0) active catalyst cannot be ignored, a mixed-ligand complex is likely present throughout the catalytic cycle. In addition, protodeborylation and hydrodehalogenation were demonstrated to be the predominant side reactions of borylation of ortho-substituted aryl halides containing the electron-deficient carboxylate substituents. Ni(II) complexes in the presence of H2O and Ni(0) are responsible for the catalysis of these side reactions.
• High-Yield Syntheses and Reactivity Studies of 1,2-Diborylated and 1,2,4,5-Tetraborylated Benzenes
  作者：Ömer Seven、Michael Bolte、Hans-Wolfram Lerner、Matthias Wagner

  DOI：10.1021/om500104w

  日期：2014.3.10

  Treatment of 1,2-dibromobenzene (1,2-C6H4Br2) or 1,2,4,5-tetrabromobenzene (1,2,4,5-C6H2Br4) with 2 equiv or 4 equiv of n-BuLi in the presence of excess iso-propoxy(pinacol)borane ((i-PrO)Bpin) furnishes 1,2-C6H4(Br)(Bpin) (1) or 1,4,2,5-C6F12(Br)(2)(Bpin)(2) (3) with excellent selectivity. The subsequent reaction of 1 or 3 with Mg turnings and more (i-PrO)Bpin gives the di- and tetraborylated benzenes 1,2-C6H4(Bpin)(2) (2) and 1,2,4,5-C6F12(Bpin)(4) (4) in overall yields of about 65%. For the Grignard transformation step, it is essential to continuously add 1 equiv (1) or 2 equiv (3) of 1,2-dibromoethane as an entrainer over a period of 1 h. Compounds 1 and 2 have been transformed into the ortho-functionalized trihydroborates Li[1,2-C6H4(Br)(BH3)] (Li[7]) and Li[1,2-C6H4(Bpin)(BH3)] (Li[8]) by means of 1 equiv of Li[AlH4]. Using 3 equiv of Li[AlH4], 2 can also be converted into the ditopic lithium trihydroborate Li-2[1,2-C6H4(BH3)(2)] (Li-2[9]); even the tetratopic derivative Li-4[1,2,4,5-C6F12(BH3)(4)] (Li-4[10]) is accessible from 4 and 4 equiv of Li[AlH4]. The compounds Li[7], Li[8], Li-2[9], and Li-4[10] have been crystallographically characterized as ether solvates, but still show Ar-BH3-eta(2)-Li interactions as the dominant mode of coordination. In the cases of Li-2[9] and Li-4[10] an intricate three-dimensional network and a zigzag polymer, respectively, are established by the contact ion pairs in the crystal lattice.
• Zero-Valent Metals Accelerate the Neopentylglycolborylation of Aryl Halides Catalyzed by NiCl₂-Based Mixed-Ligand Systems
  作者：Pawaret Leowanawat、Ana-Maria Resmerita、Costel Moldoveanu、Chi Liu、Na Zhang、Daniela A. Wilson、Lisa M. Hoang、Brad M. Rosen、Virgil Percec

  DOI：10.1021/jo101718v

  日期：2010.11.19

  The highly active mixed-ligand catalytic system NiCl2(dppp)/dppf combined with the reducing effect of zerovalent Zn and of other metals was used to demonstrate a method for the dramatic acceleration of the rate and for the enhancement of the yield of Ni-catalyzed neopentylglycolborylation of aryl halides A diversity of electron-rich and electron-deficient aryl iodides, bromides, and chlorides were efficiently neopentylglycolborylated, typically in 1 h or less This acceleration is particularly remarkable for the generally less reactive aryl bromides and chlorides and for all ortho-substituted aryl halides By accelerating the rate of borylation and reducing its reaction time to complete conversion, pathways leading to protodeborylated or hydrodehalogenated side products have a reduced impact on the outcome of the overall reaction Although Zn powder was the reducing agent of choice, compatibility of this technique with more readily recoverable Zn chips, as well as other metals such as Mn, Mg, Fe, Al, and Ca, has demonstrated the broad scope of this synthetic method