2-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-benzoic acid methyl ester

• 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: 2-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-benzoic acid methyl ester
• 英文别名: methyl 2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzoate
• 化学式: C₁₃H₁₇BO₄
• 分子量: 248.087
• InChiKey: FIIRHYAXUYGUTA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.24
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-benzoic acid methyl ester 在 二氟化氢钾 作用下， 以 甲醇 、 水 为溶剂， 生成 potassium trifluoro(2-(methoxycarbonyl)phenyl)borate
  参考文献：
  名称：

  Neopentylglycolborylation of ortho-Substituted Aryl Halides Catalyzed by NiCl₂-Based Mixed-Ligand Systems

  摘要：

  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.

  DOI：

  10.1021/jo101023t
• 作为产物：
  描述：

  2-氯苯甲酸甲酯 、 neopentylglycolborane 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 1.0h， 以95%的产率得到2-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-benzoic acid methyl ester
  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

• <i>trans</i>-Chloro(1-Naphthyl)bis(triphenylphosphine)nickel(II)/PCy₃ Catalyzed Cross-Coupling of Aryl and Heteroaryl Neopentylglycolboronates with Aryl and Heteroaryl Mesylates and Sulfamates at Room Temperature
  作者：Pawaret Leowanawat、Na Zhang、Mehtap Safi、David J. Hoffman、Miriam C. Fryberger、Aiswaria George、Virgil Percec

  DOI：10.1021/jo3001194

  日期：2012.3.16

  been successfully applied as catalyst for the Suzuki–Miyaura cross-coupling of aryl and heteroaryl neopentylglycolboronates with aryl and heteroaryl mesylates and sulfamates in THF at room temperature. This cross-coupling reaction tolerates various functional groups, including keto, imino, ester, ether, and cyano. Together with the nickel-catalyzed, one-pot, two-step neopentylglycolborylation, this bench

  反式-氯（1-萘基）双（三苯基膦）镍（II）配合物/ PCy 3体系已成功用作Suzuki-Miyaura的芳烃和杂芳基新戊二醇硼酸酯与芳基和杂芳基甲磺酸酯和氨基磺酸酯的Suzuki-Miyaura交叉偶联室内温度。这种交叉偶联反应可耐受各种官能团，包括酮基，亚氨基，酯基，醚基和氰基。与镍催化的一锅两步新戊基糖基化反应一起使用，这种台式稳定且廉价的Ni（II）基催化剂可以用作Ni（COD）2 / PCy 3的替代品，从而提供廉价，坚固，方便地合成联芳基和杂联芳基化合物。
• An efficient synthesis of sterically hindered arylboronic acids
  作者：Hao Fang、Gurpreet Kaur、Jun Yan、Binghe Wang

  DOI：10.1016/j.tetlet.2005.01.064

  日期：2005.3

  variety of applications. In our research, we have found that the synthesis of ortho-substituted arylboronic acids is problematic with the commonly used bis(pinacolato)diboron in palladium-mediated borylation reactions. As a substitute, we have found that bis(neopentyl glycolato)diboron is a much more efficient borylation agent for the synthesis of sterically hindered ortho-substituted arylboronic acids.

  硼酸是广泛应用中的重要中间体和分子识别部分。在我们的研究中，我们发现邻位取代的芳基硼酸的合成对于钯介导的硼化反应中常用的双（频哪醇）二硼是有问题的。作为替代品，我们发现双（新戊基乙二醇基）二硼是用于合成位阻邻位取代的芳基硼酸的更有效的硼化剂。
• Neopentylglycolborylation of Aryl Mesylates and Tosylates Catalyzed by Ni-Based Mixed-Ligand Systems Activated with Zn
  作者：Daniela A. Wilson、Christopher J. Wilson、Costel Moldoveanu、Ana-Maria Resmerita、Patrick Corcoran、Lisa M. Hoang、Brad M. Rosen、Virgil Percec

  DOI：10.1021/ja910808x

  日期：2010.2.17

  The mixed-ligand system NiCl2(dppp)/dppf is shown to be an effective catalyst for the neopentylglycolborylation of ortho-, meta-, and para- substituted electron-rich and electron-deficient aryl mesylates and tosylates. The addition of Zn powder as a reductant dramatically increases the reaction yield and reduces the reaction time by more than an order of magnitude, providing complete conversion in 1-3 h
• Ni(COD)₂/PCy₃ Catalyzed Cross-Coupling of Aryl and Heteroaryl Neopentylglycolboronates with Aryl and Heteroaryl Mesylates and Sulfamates in THF at Room Temperature
  作者：Pawaret Leowanawat、Na Zhang、Ana-Maria Resmerita、Brad M. Rosen、Virgil Percec

  DOI：10.1021/jo202037x

  日期：2011.12.16

  Reaction conditions for the Ni(COD)(2)/PCy3 catalyzed cross-coupling of aryl neopentylglycolboronates with aryl mesylates were developed. By using optimized reaction conditions, Ni(COD)(2)/PCy3 was shown to be a versatile catalyst for the cross-coupling of a diversity of aryl neopentylglycolboronates with aryl and heteroaryl mesylates and sulfamates containing both electron-donating and electron-withdrawing substituents in their para, ortho, and meta positions in THF at room temperature. This Ni-catalyzed cross-coupling of aryl neopentylglycolboronates is also effective for the synthesis of heterobiaryls and biaryls containing electrophilic functionalities sensitive to organolithium and organomagnesium derivatives. In combination with the recently developed Ni-catalyzed neopentylglycolborylation, all Ni-catalyzed routes to functional biaryls and heterobiaryls are now easily accessible.