2,6-difluorophenylboronic acid neopentyl glycol ester | 1239569-27-7

• 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: 2,6-difluorophenylboronic acid neopentyl glycol ester
• 英文别名: 2-(2,6-Difluorophenyl)-5,5-dimethyl-1,3,2-dioxaborinane
• CAS: 1239569-27-7
• 化学式: C₁₁H₁₃BF₂O₂
• 分子量: 226.031
• InChiKey: UUZFUNZCNAULPI-UHFFFAOYSA-N

物化性质

• 熔点：
  42-44 °C
• 沸点：
  286.6±30.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.73
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,6-difluorophenylboronic acid neopentyl glycol ester 在 三氟乙酸 、 potassium hydroxide 作用下， 以 1,4-二氧六环 、 乙醚 、 水 为溶剂， 生成 1,3-二氟苯
  参考文献：
  名称：

  （杂）芳基硼酸酯的原脱硼：直接与预水解途径和自/自催化

  摘要：

  一系列硼酸酯的碱催化水解（ArB(OR) 2 → ArB(OH) 2）和原脱硼化（ArB(OR) 2 → ArH）的动力学和机理，包括八种不同的多元醇和 10 种多氟芳基和杂芳基部分，已通过原位和停流 NMR 光谱（19 F、1 H 和11 B）、pH 速率依赖性、同位素夹带进行了研究，2H KIE 和 KS-DFT 计算。该研究揭示了硼酸酯在碱性水-有机条件下的现象稳定性非常微妙。与通常的假设相反，与相应的硼酸相比，酯化不一定赋予更高的稳定性。此外，酯水解为硼酸可以是整个原脱硼过程的主要成分，当 pH 值接近硼酸的 p K a时，自催化、自催化和氧化（酚类）催化作用增强酯。

  DOI：

  10.1021/jacs.1c06863
• 作为产物：
  描述：

  2,2-二甲基-1,3-丙二醇 、 2,6-二氟苯硼酸 以 乙醚 为溶剂， 生成 2,6-difluorophenylboronic acid neopentyl glycol ester
  参考文献：
  名称：

  金催化有机金属的氧化联芳基交叉偶联

  摘要：

  联芳基亲核试剂之间的偶联（AR δ-：arylboronates或芳基硅烷）和亲电（AR δ+：芳基卤化物）代表了碳-碳键形成的最新技术。这些反应中固有的官能团限制源于钯和镍催化剂对卤素，硼酸酯和碱敏感取代基的高催化反应性。在这里，我们报告了一般的二聚体金催化的芳基硼酸酯和芳基硅烷的氧化交叉偶联反应，而没有用于合成的外部碱，具有不对称联芳基的优异的官能团耐受性。两种偶合剂均易于获得，稳定且无毒。各种各样的（假）卤代和硼化偶合剂可以成功地应用于这种位点特定的联芳基偶合剂，具有前所未有的多功能性。简明地制备几种π共轭有机材料和药效基团已证实了其合成价值。

  DOI：

  10.1016/j.chempr.2019.07.023

文献信息

• Gold Catalyzed Decarboxylative Cross-Coupling of Iodoarenes
  作者：Ryan A. Daley、Aaron S. Morrenzin、Sharon R. Neufeldt、Joseph J. Topczewski

  DOI：10.1021/jacs.0c06244

  日期：2020.7.29

  This report details a decarboxylative cross-coupling of (hetero)aryl carboxylates with iodoarenes in the presence of a gold cata-lyst (>25 examples, up to 96% yield). This reaction is site specific, which overcomes prior limitations associated with gold cat-alyzed oxidative coupling reactions. The reactivity of the (hetero)aryl carboxylate correlates qualitatively to the field effect pa-rameter (Fortho)

  该报告详细介绍了（杂）芳基羧酸酯与碘芳烃在金催化剂存在下的脱羧交叉偶联（> 25 个例子，产率高达 96%）。该反应是位点特异性的，它克服了与金催化氧化偶联反应相关的先前限制。(杂)芳基羧酸酯的反应性与场效应参数(Fortho)定性相关。与分离的金配合物的反应和 DFT 计算支持通过在金 (I) 阳离子上氧化加成进行的机制，脱羧在金 (I) 或银 (I) 物种中都是可行的。
• 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
• 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.
• Protodeboronation of (Hetero)Arylboronic Esters: Direct versus Prehydrolytic Pathways and Self-/Auto-Catalysis
  作者：Hannah L. D. Hayes、Ran Wei、Michele Assante、Katherine J. Geogheghan、Na Jin、Simone Tomasi、Gary Noonan、Andrew G. Leach、Guy C. Lloyd-Jones

  DOI：10.1021/jacs.1c06863

  日期：2021.9.15

  boronic esters under basic aqueous–organic conditions to be highly nuanced. In contrast to common assumption, esterification does not necessarily impart greater stability compared to the corresponding boronic acid. Moreover, hydrolysis of the ester to the boronic acid can be a dominant component of the overall protodeboronation process, augmented by self-, auto-, and oxidative (phenolic) catalysis when

  一系列硼酸酯的碱催化水解（ArB(OR) 2 → ArB(OH) 2）和原脱硼化（ArB(OR) 2 → ArH）的动力学和机理，包括八种不同的多元醇和 10 种多氟芳基和杂芳基部分，已通过原位和停流 NMR 光谱（19 F、1 H 和11 B）、pH 速率依赖性、同位素夹带进行了研究，2H KIE 和 KS-DFT 计算。该研究揭示了硼酸酯在碱性水-有机条件下的现象稳定性非常微妙。与通常的假设相反，与相应的硼酸相比，酯化不一定赋予更高的稳定性。此外，酯水解为硼酸可以是整个原脱硼过程的主要成分，当 pH 值接近硼酸的 p K a时，自催化、自催化和氧化（酚类）催化作用增强酯。
• Gold-Catalyzed Oxidative Biaryl Cross-Coupling of Organometallics
  作者：Kai Liu、Nian Li、Yunyun Ning、Chengjian Zhu、Jin Xie

  DOI：10.1016/j.chempr.2019.07.023

  日期：2019.10

  without an external base for the synthesis, with excellent functional-group tolerance of asymmetric biaryls. Both coupling partners are readily available, bench-stable, and non-toxic. A broad array of (pseudo)halogenated and borylated coupling partners can be successfully applied to this site-specific biaryl coupling with unprecedented versatility. Its synthetic value has been substantiated by concise preparation

  联芳基亲核试剂之间的偶联（AR δ-：arylboronates或芳基硅烷）和亲电（AR δ+：芳基卤化物）代表了碳-碳键形成的最新技术。这些反应中固有的官能团限制源于钯和镍催化剂对卤素，硼酸酯和碱敏感取代基的高催化反应性。在这里，我们报告了一般的二聚体金催化的芳基硼酸酯和芳基硅烷的氧化交叉偶联反应，而没有用于合成的外部碱，具有不对称联芳基的优异的官能团耐受性。两种偶合剂均易于获得，稳定且无毒。各种各样的（假）卤代和硼化偶合剂可以成功地应用于这种位点特定的联芳基偶合剂，具有前所未有的多功能性。简明地制备几种π共轭有机材料和药效基团已证实了其合成价值。