2-(3-bromo-4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 1394130-69-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-(3-bromo-4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 1394130-69-8
• 化学式: C₁₃H₁₈BBrO₃
• 分子量: 312.999
• InChiKey: BIZJYDBUTILINW-UHFFFAOYSA-N

物化性质

• 沸点：
  365.0±32.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.76
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(3-bromo-4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 三氯化硼 、 溶剂黄146 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 24.5h， 生成 2-溴苯甲醚
  参考文献：
  名称：

  Metal-Free Protodeboronation of Electron-Rich Arene Boronic Acids and Its Application to ortho-Functionalization of Electron-Rich Arenes Using a Boronic Acid as a Blocking Group

  摘要：

  The metal-free thermal protodeboronation of various electron-rich arene boronic acids was studied. Several reaction parameters controlling this protodeboronation, such as solvent, temperature, and a proton source, have been investigated. On the basis of these studies, suitable reaction conditions for protodeboronation of several types of electron-rich arene boronic acids were provided. On the basis of this protodeboronation, a new protocol for the synthesis of ortho-functionalized electron-rich arenes from these boronic acids was developed using the boronic acid moiety as a blocking group in the electrophilic aromatic substitution reaction, followed by the removal of the boronic acid moiety via thermal protodeboronation. Mechanistic studies suggested that this protodeboronation might proceed via the complex formation of a boronic acid with a proton source, followed by the carbon-boron bond fission through σ-bond metathesis, to afford the corresponding arene compound and boric acid.

  DOI：

  10.1021/jo500780b
• 作为产物：
  描述：

  4-甲氧基苯硼酸频那醇酯 在 溴 作用下， 以 二氯甲烷 为溶剂， 以70%的产率得到2-(3-bromo-4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  全合成阿凡韦洛尔

  摘要：

  报道了海洋天然产物阿夫那韦尔的首次全合成。总合成的特征是将甲苯磺酰和硼酸的无过渡金属的偶联首次用于制备复杂的天然产物，以及该偶联与受阻二邻位取代substrate底物的偶联的第一个实例。

  DOI：

  10.1021/acs.joc.7b02028

文献信息

• Catalyst-Free C(sp²)-H Borylation through Aryl Radical Generation from Thiophenium Salts via Electron Donor–Acceptor Complex Formation
  作者：Bo Li、Ke Wang、Huifeng Yue、Alwin Drichel、Jingjing Lin、Zhenying Su、Magnus Rueping

  DOI：10.1021/acs.orglett.2c03008

  日期：2022.10.14

  of base, transition metal–ligand complex, or photoredox catalyst. Mechanistic studies reveal that this transformation is achieved through an electron donor–acceptor (EDA) complex activation in the absence of a catalyst. The mild reaction conditions allow the preparation of aromatic borates in good yields with excellent functional group tolerance. This photochemical protocol was also successfully applied

  芳基硼酸酯是碳-碳键偶联的核心，广泛应用于功能材料、药物化合物和天然产物的合成。目前，芳基硼酸酯的合成方法大多局限于金属催化路线，非金属策略仍相对欠发达。在此，我们报告了在没有碱基、过渡金属-配体络合物或光氧化还原催化剂。机理研究表明，这种转化是在没有催化剂的情况下通过电子供体-受体 (EDA) 复合物活化实现的。温和的反应条件允许以良好的收率制备芳族硼酸酯，并具有优异的官能团耐受性。该光化学方案还成功应用于天然产物的后期修饰和药物中间体的合成，极大地展示了广泛的实用性。
• Transition-Metal-Free Borylation of Aryltriazene Mediated by BF₃·OEt₂
  作者：Chuan Zhu、Motoki Yamane

  DOI：10.1021/ol302024m

  日期：2012.9.7

  A practical and simple method for deaminoborylation of aryltriazene with bis(pinacolato)diboron has been developed that is mediated by BF3 center dot OEt2. Various arylboronic esters are prepared in moderate to good yields with this facile transition-metal-free procedure.
• Discovery of a 2,6-diarylpyridine-based hydroxamic acid derivative as novel histone deacetylase 8 and tubulin dual inhibitor for the treatment of neuroblastoma
  作者：Hairong Tang、Yuru Liang、Hanchen Shen、Shaowen Cai、Min Yu、Hongrui Fan、Kuiling Ding、Yang Wang

  DOI：10.1016/j.bioorg.2022.106112

  日期：2022.11
• Metal-Free Protodeboronation of Electron-Rich Arene Boronic Acids and Its Application to <i>ortho</i>-Functionalization of Electron-Rich Arenes Using a Boronic Acid as a Blocking Group
  作者：Su-Jin Ahn、Chun-Young Lee、Nak-Kyoon Kim、Cheol-Hong Cheon

  DOI：10.1021/jo500780b

  日期：2014.8.15

  The metal-free thermal protodeboronation of various electron-rich arene boronic acids was studied. Several reaction parameters controlling this protodeboronation, such as solvent, temperature, and a proton source, have been investigated. On the basis of these studies, suitable reaction conditions for protodeboronation of several types of electron-rich arene boronic acids were provided. On the basis of this protodeboronation, a new protocol for the synthesis of ortho-functionalized electron-rich arenes from these boronic acids was developed using the boronic acid moiety as a blocking group in the electrophilic aromatic substitution reaction, followed by the removal of the boronic acid moiety via thermal protodeboronation. Mechanistic studies suggested that this protodeboronation might proceed via the complex formation of a boronic acid with a proton source, followed by the carbon-boron bond fission through σ-bond metathesis, to afford the corresponding arene compound and boric acid.
• Total Synthesis of Avrainvilleol
  作者：Aaron Wegener、Kenneth A. Miller

  DOI：10.1021/acs.joc.7b02028

  日期：2017.11.3

  The first total synthesis of the marine natural product avrainvilleol is reported. The total synthesis features the first application of the transition-metal-free coupling of a tosyl hydrazone and a boronic acid to the preparation of a complex natural product, and the first example of this coupling with a hindered diortho substituted hydrazone substrate.

  报道了海洋天然产物阿夫那韦尔的首次全合成。总合成的特征是将甲苯磺酰和硼酸的无过渡金属的偶联首次用于制备复杂的天然产物，以及该偶联与受阻二邻位取代substrate底物的偶联的第一个实例。