2-bromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 2-bromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol
• 英文别名: 2-Bromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-YL)phenol
• 化学式: C₁₂H₁₆BBrO₃
• 分子量: 298.972
• InChiKey: GTOCGUJYNAWCHI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.45
• 重原子数：
  17
• 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：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-bromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol 以 水 、 二甲基亚砜 为溶剂， 反应 24.0h， 以0.3 g的产率得到2-溴苯酚
  参考文献：
  名称：

  Protodeboronation of ortho- and para-Phenol Boronic Acids and Application to ortho and meta Functionalization of Phenols Using Boronic Acids as Blocking and Directing Groups

  摘要：

  The first metal-free thermal protodeboronation of ortho- and para-phenol boronic acids in DMSO was developed. The protodeboronation was successfully applied to the synthesis of ortho- and meta-functionalized phenols using the boronic acid moiety as a blocking group and a directing group, respectively. Mechanistic studies suggested that this protodeboronation proceeds through the coordination of water to the boron atom followed by sigma-bond metathesis.

  DOI：

  10.1021/jo402174v
• 作为产物：
  描述：

  4-羟基苯硼酸频哪醇酯 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 2-bromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol
  参考文献：
  名称：

  Protodeboronation of ortho- and para-Phenol Boronic Acids and Application to ortho and meta Functionalization of Phenols Using Boronic Acids as Blocking and Directing Groups

  摘要：

  The first metal-free thermal protodeboronation of ortho- and para-phenol boronic acids in DMSO was developed. The protodeboronation was successfully applied to the synthesis of ortho- and meta-functionalized phenols using the boronic acid moiety as a blocking group and a directing group, respectively. Mechanistic studies suggested that this protodeboronation proceeds through the coordination of water to the boron atom followed by sigma-bond metathesis.

  DOI：

  10.1021/jo402174v

文献信息

• <i>Para</i>-Selective C–H Borylation of Common Arene Building Blocks Enabled by Ion-Pairing with a Bulky Countercation
  作者：Madalina T. Mihai、Benjamin D. Williams、Robert J. Phipps

  DOI：10.1021/jacs.9b07267

  日期：2019.10.2

  The selective functionalization of C–H bonds at the arene para position is highly challenging using transition metal catalysis. Iridium-catalyzed borylation has emerged as a leading technique for arene functionalization, but there are only a handful of strategies for para-selective borylation, which operate on specific substrate classes and use bespoke ligands or catalysts. We describe a remarkably

  使用过渡金属催化对芳烃对位的 C-H 键进行选择性官能化是非常具有挑战性的。铱催化硼化已成为芳烃功能化的领先技术，但对位选择性硼化的策略很少，它们在特定的底物类别上运行并使用定制的配体或催化剂。我们描述了一个非常通用的协议，它导致对一些最常见的芳烃构建块（苯胺、苄胺、苯酚、苄醇）产生对位选择性，并使用标准硼酸化配体。我们的策略取决于将底物轻松转化为硫酸盐或氨基磺酸盐，其中阴离子芳烃组分与四丁基铵阳离子配对。我们假设该阳离子的大部分不利于间位 C-H 硼酸化，
• Para-Selective, Iridium-Catalyzed C–H Borylations of Sulfated Phenols, Benzyl Alcohols, and Anilines Directed by Ion-Pair Electrostatic Interactions
  作者：Jose R. Montero Bastidas、Thomas J. Oleskey、Susanne L. Miller、Milton R. Smith、Robert E. Maleczka

  DOI：10.1021/jacs.9b08464

  日期：2019.10.2

  Para C-H borylation (CHB) of tetraalkylammonium sulfates and sulfamates have been achieved using bipyridne-ligated Ir boryl catalysts. Selectivities can be modulated both by the length of the alkyl groups in the tetraalkylammonium cations and the substituents on the bipyridine ligands. Ion-pairing, where the alkyl groups of the cation shield the meta C-H bonds in the conteranions, is proposed to account

  四烷基硫酸铵和氨基磺酸盐的对位 CH 硼化 (CHB) 已使用联吡啶连接的 Ir boryl 催化剂实现。选择性可以通过四烷基铵阳离子中烷基的长度和联吡啶配体上的取代基来调节。离子对，其中阳离子的烷基屏蔽了对位离子中的间位 CH 键，被认为是对位选择性的原因。4,4'-二甲氧基-2,2'-联吡啶配体具有优异的选择性。
• Protodeboronation of ortho- and para-Phenol Boronic Acids and Application to ortho and meta Functionalization of Phenols Using Boronic Acids as Blocking and Directing Groups
  作者：Chun-Young Lee、Su-Jin Ahn、Cheol-Hong Cheon

  DOI：10.1021/jo402174v

  日期：2013.12.6

  The first metal-free thermal protodeboronation of ortho- and para-phenol boronic acids in DMSO was developed. The protodeboronation was successfully applied to the synthesis of ortho- and meta-functionalized phenols using the boronic acid moiety as a blocking group and a directing group, respectively. Mechanistic studies suggested that this protodeboronation proceeds through the coordination of water to the boron atom followed by sigma-bond metathesis.