2-(1-naphthyl)[1,3,2]dioxaborolane | 919988-32-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-(1-naphthyl)[1,3,2]dioxaborolane
• 英文别名: 2-(Naphthalen-2-yl)-1,3,2-dioxaborolane；2-naphthalen-2-yl-1,3,2-dioxaborolane
• CAS: 919988-32-2
• 化学式: C₁₂H₁₁BO₂
• 分子量: 198.029
• InChiKey: LFAPCYMYTSETAW-UHFFFAOYSA-N

物化性质

• 沸点：
  375.0±11.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.58
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(1-naphthyl)[1,3,2]dioxaborolane 在 caesium carbonate 、 2,4-二硝基苯基羟胺 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 24.0h， 以73%的产率得到2-萘胺
  参考文献：
  名称：

  Elusive Metal-Free Primary Amination of Arylboronic Acids: Synthetic Studies and Mechanism by Density Functional Theory

  摘要：

  Herein, we disclose the first metal-free synthesis of primary aromatic amines from arylboronic acids, a reaction that has eluded synthetic chemists for decades. This remarkable transformation affords structurally diverse primary arylamines in good chemical yields, including a variety of halogenated primary anilines that often cannot be prepared via transition-metal-catalyzed amination. The reaction is operationally simple, requires only a slight excess of aminating agent, proceeds under neutral or basic conditions, and, importantly, can be scaled up to provide multigram quantities of primary anilines. Density functional calculations reveal that the most likely mechanism involves a facile 1,2-aryl migration and that the presence of an ortho nitro group in the aminating agent plays a critical role in lowering the free energy barrier of the 1,2-aryl migration step.

  DOI：

  10.1021/ja309637r
• 作为产物：
  描述：

  1-溴代萘 、 乙二醇 在 magnesium 、 硼酸三甲酯 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 以85%的产率得到2-(1-naphthyl)[1,3,2]dioxaborolane
  参考文献：
  名称：

  制备芳基硼酸酯的高效便捷的非水后处理程序。

  摘要：

  已经建立了用于合成芳基硼酸酯的有效的一锅合成方案。用低分子量二醇（乙二醇，1，3-丙二醇）和甲苯处理硼酸三甲酯与芳基格氏试剂的浓缩加成混合物，以方便的方式高产率地分离出相应的芳基硼酸酯。二醇不仅用作后处理步骤的水替代物，而且还用作制备芳基硼酸酯的试剂。

  DOI：

  10.1021/jo011073j

文献信息

• Pd‐Catalyzed Difluoromethylations of Aryl Boronic Acids, Halides, and Pseudohalides with ICF ₂ H Generated ex Situ
  作者：Oliver R. Gedde、Andreas Bonde、Peter I. Golbækdal、Troels Skrydstrup

  DOI：10.1002/chem.202200997

  日期：2022.6.15

  ex-situ generation of difluoroiodomethane (DFIM) and its immediate use in a Pd-catalyzed difluoromethylation of aryl boronic acids and ester derivatives in a two-chamber reactor is reported. Heating a solution of bromodifluoroacetic acid with sodium iodide in sulfolane proved to be effective for the generation of near stoichiometric amounts of DFIM for the ensuing catalytic coupling step. A two-step difluoromethylation

  据报道，二氟碘甲烷（DFIM）的便捷异位生成及其在双室反应器中钯催化的芳基硼酸和酯衍生物的二氟甲基化中的直接应用。事实证明，加热溴二氟乙酸与碘化钠的环丁砜溶液可有效生成接近化学计量的 DFIM，用于随后的催化偶联步骤。芳基（拟）卤化物与四羟基二硼作为低成本还原剂的两步二氟甲基化，均由 Pd 催化促进，被证明可以有效地将这种含氟 C1 基团安装到几个药物相关分子上。最后，通过简单地将 D2 O 添加到 DFIM 生成室，该方法被证明适用于氘掺入。
• Elusive Metal-Free Primary Amination of Arylboronic Acids: Synthetic Studies and Mechanism by Density Functional Theory
  作者：Chen Zhu、Gongqiang Li、Daniel H. Ess、John R. Falck、László Kürti

  DOI：10.1021/ja309637r

  日期：2012.11.7

  Herein, we disclose the first metal-free synthesis of primary aromatic amines from arylboronic acids, a reaction that has eluded synthetic chemists for decades. This remarkable transformation affords structurally diverse primary arylamines in good chemical yields, including a variety of halogenated primary anilines that often cannot be prepared via transition-metal-catalyzed amination. The reaction is operationally simple, requires only a slight excess of aminating agent, proceeds under neutral or basic conditions, and, importantly, can be scaled up to provide multigram quantities of primary anilines. Density functional calculations reveal that the most likely mechanism involves a facile 1,2-aryl migration and that the presence of an ortho nitro group in the aminating agent plays a critical role in lowering the free energy barrier of the 1,2-aryl migration step.
• Efficient and Convenient Nonaqueous Workup Procedure for the Preparation of Arylboronic Esters
  作者：Ken-Tsung Wong、Yuh-Yih Chien、Yuan-Li Liao、Chang-Chih Lin、Meng-Yen Chou、Man-kit Leung

  DOI：10.1021/jo011073j

  日期：2002.2.1

  An efficient one-pot synthetic protocol for the synthesis of arylboronic esters has been established. The concentrated addition mixture of trimethylborate with aryl Grignard reagents was treated with low molecular weight diols (ethylene glycol, 1,3-propandiol) and toluene, the corresponding arylboronic esters were isolated in a convenient way with high yields. The diols not only serve as water replacement

  已经建立了用于合成芳基硼酸酯的有效的一锅合成方案。用低分子量二醇（乙二醇，1，3-丙二醇）和甲苯处理硼酸三甲酯与芳基格氏试剂的浓缩加成混合物，以方便的方式高产率地分离出相应的芳基硼酸酯。二醇不仅用作后处理步骤的水替代物，而且还用作制备芳基硼酸酯的试剂。