4,4,5,5-tetramethyl-2-(2,4,5-trifluorophenyl)-1,3,2-dioxaborolane

• 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: 4,4,5,5-tetramethyl-2-(2,4,5-trifluorophenyl)-1,3,2-dioxaborolane
• 英文别名: 4,4,5,5-Tetramethyl-2-(2,4,5-trifluorophenyl)-1,3,2-dioxaborolane
• 化学式: C₁₂H₁₄BF₃O₂
• 分子量: 258.048
• InChiKey: SHTZNQIDIDKSNW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1,2,4,5-四氟苯 、 联硼酸频那醇酯 在 Ni(1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene)2 、 四甲基氟化铵 作用下， 以 甲基环己烷 为溶剂， 反应 15.0h， 以70%的产率得到4,4,5,5-tetramethyl-2-(2,4,5-trifluorophenyl)-1,3,2-dioxaborolane
  参考文献：
  名称：

  Preparing (Multi)Fluoroarenes as Building Blocks for Synthesis: Nickel-Catalyzed Borylation of Polyfluoroarenes via C–F Bond Cleavage

  摘要：

  The [Ni(IMes)(2)]-catalyzed transformation of fluoroarenes into arylboronic acid pinacol esters via C-F bond activation and transmetalation with bis(pinacolato)diboron (B(2)pin(2)) is reported. Various partially fluorinated arenes with different degrees of fluorination were converted into their corresponding boronate esters.

  DOI：

  10.1021/jacs.6b02337

文献信息

• Selective Photocatalytic C–F Borylation of Polyfluoroarenes by Rh/Ni Dual Catalysis Providing Valuable Fluorinated Arylboronate Esters
  作者：Ya-Ming Tian、Xiao-Ning Guo、Maximilian W. Kuntze-Fechner、Ivo Krummenacher、Holger Braunschweig、Udo Radius、Andreas Steffen、Todd B. Marder

  DOI：10.1021/jacs.8b09790

  日期：2018.12.19

  B2pin2 at room temperature in excellent yields and with high selectivity. Direct irradiation of the intermediary C-F bond oxidative addition product trans-[NiF(ArF)(IMes)2] leads to very fast decomposition when B2pin2 is present. This destructive pathway can be bypassed by indirect excitation of the triplet states of the nickel(II) complex via the photoexcited rhodium biphenyl complex. Mechanistic studies

  一种高选择性和通用的光催化 CF 硼化方案，采用联苯铑配合物作为三线态敏化剂和镍催化剂 [Ni(IMes)2] (IMes = 1,3-dimesityliimidazoline-2-ylidene) 用于 CF 键活化和脱氟硼酸化过程被报告。这种串联催化剂系统在可见光（蓝色，400 nm）下运行，并在室温下以高产率和高选择性实现了多种氟芳烃与 B2pin2 的硼化。当存在 B2pin2 时，直接照射中间 CF 键氧化加成产物反式-[NiF(ArF)(IMes)2] 会导致非常快速的分解。这种破坏性途径可以通过光激发的铑联苯络合物间接激发镍 (II) 络合物的三重态来绕过。机理研究表明，用作光敏剂的 Rh 联苯配合物的超长寿命三线态激发态允许有效的三线态能量转移到反式 [NiF(ArF)(IMes)2]，从而导致 NHC 之一的解离配体。这与目前大多数采用过渡金属作为激发态单电子转移剂的光催化转化形成对比。我们之前曾报道过
• Fluorine-controlled C–H borylation of arenes catalyzed by a PSiN-pincer platinum complex
  作者：Jun Takaya、Shisei Ito、Hironori Nomoto、Narumasa Saito、Naohiro Kirai、Nobuharu Iwasawa

  DOI：10.1039/c5cc07263h

  日期：——

  Fluorine-controlled C–H borylation of fluoroarenes catalyzed by a PSiN–platinum complex.

  氟控制的PSiN-铂配合物催化的氟芳烃C-H硼化反应。
• Iridium‐Catalysed C−H Borylation of Fluoroarenes: Insights into the Balance between Steric and Electronic Control of Regioselectivity
  作者：Mingyan Ding、Jonathan A. Reuven、Andrew C. Hones、Mark A. Fox、Patrick G. Steel

  DOI：10.1002/ejoc.202201005

  日期：2022.12.19

  Iridium catalysed C−H borylation provides an effective method for late stage functionalization of fluorinated arenes and heteroarenes. The reaction occurs rapidly and efficiently with selectivity that can be best predicted using computed relative transition stage energies.

  铱催化的 C−H 硼酸化为氟化芳烃和杂芳烃的后期功能化提供了一种有效的方法。反应快速有效地发生，选择性可以使用计算的相对过渡阶段能量进行最佳预测。
• Preparing (Multi)Fluoroarenes as Building Blocks for Synthesis: Nickel-Catalyzed Borylation of Polyfluoroarenes via C–F Bond Cleavage
  作者：Jing Zhou、Maximilian W. Kuntze-Fechner、Rüdiger Bertermann、Ursula S. D. Paul、Johannes H. J. Berthel、Alexandra Friedrich、Zhenting Du、Todd B. Marder、Udo Radius

  DOI：10.1021/jacs.6b02337

  日期：2016.4.27

  The [Ni(IMes)(2)]-catalyzed transformation of fluoroarenes into arylboronic acid pinacol esters via C-F bond activation and transmetalation with bis(pinacolato)diboron (B(2)pin(2)) is reported. Various partially fluorinated arenes with different degrees of fluorination were converted into their corresponding boronate esters.