5-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-N,N-dimethylbenzylamine | 1349171-43-2

• 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: 5-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-N,N-dimethylbenzylamine
• 英文别名: N,N-dimethyl-1-[5-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]methanamine；N,N-dimethyl-1-(5-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanamine
• CAS: 1349171-43-2
• 化学式: C₁₆H₂₆BNO₂
• 分子量: 275.199
• InChiKey: WJYSQHPVKKBNHQ-UHFFFAOYSA-N

物化性质

• 熔点：
  86.6-88.8 °C
• 沸点：
  353.3±37.0 °C(predicted)
• 密度：
  0.99±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.36
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  21.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-N,N-dimethylbenzylamine 在 potassium fluoride 、 氧气 、 copper(II) acetate monohydrate 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以40%的产率得到1,1'-(4,4'-dimethyl-[1,1'-biphenyl]-2,2'-diyl)bis(N,N-dimethylmethanamine)
  参考文献：
  名称：

  铜催化硼酸苄胺硼酸酯的选择性催化形成邻氨基苄胺

  摘要：

  已经研究了苄基氨基硼酸酯和芳基胺之间的铜催化偶联。邻位形成在乙酸铜（II）的存在下，在氧化条件下获得-氨基苄胺。转化的主要副产物是芳基硼酸酯的均偶联。发现在不存在碱的情况下所需二胺的形成得到改善，相对于均偶联产物增加了选择性。在反应条件下，在硼酸酯底物和苯胺偶联配偶体上都可以同时接受给电子和吸电子取代基。相邻苄胺基团的存在似乎增强了硼酸酯的反应性并影响了最终产物的分布，这可能是通过影响催化循环中金属转移的竞争速率来实现的。

  DOI：

  10.1021/acs.joc.5b01074
• 作为产物：
  描述：

  N,N-二甲基氨基甲基-1-甲基-4-苯 、 联硼酸频那醇酯 在 catalyst: [Rh(OCH₃)((CHCHC₂H₄)2)]2/Silica-SMAP 作用下， 以 正己烷 为溶剂， 以99%的产率得到5-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-N,N-dimethylbenzylamine
  参考文献：
  名称：

  Rh-Catalyzed Ortho-Selective C–H Borylation of N-Functionalized Arenes with Silica-Supported Bridgehead Monophosphine Ligands

  摘要：

  Supported phosphine-Rh systems, prepared in situ from silica-supported bridgehead monophosphines and [Rh(OH)(cod)]2, have enabled ortho-selective C-H borylation for a range of arenes containing nitrogen-based directing groups. The regioselectivity was excellent with various N-directing groups, including saturated and unsaturated N-heterocycles, tert-aminoalkyl groups, and iminetype C-N double bonds. The reaction showed significant tolerance toward steric repulsion around the reacting C-H bond. This Rh catalysis complements the Jr-catalyzed orthoborylation, which is effective for arenes with oxygen-based directing groups.

  DOI：

  10.1021/ja208364a

文献信息

• Iridium-Catalyzed, Substrate-Directed C–H Borylation Reactions of Benzylic Amines
  作者：Andrew J. Roering、Lillian V. A. Hale、Phillip A. Squier、Marissa A. Ringgold、Emily R. Wiederspan、Timothy B. Clark

  DOI：10.1021/ol301635x

  日期：2012.7.6

  The iridium-catalyzed arene C–H borylation reaction of benzylic amines has been developed, which inverts the typical steric-controlled product distribution to provide ortho-substituted boronate esters. Picolylamine was found to be an ideal ligand to replace 4,4′-di-tert-butylbipyridine to induce the directing effect. Preliminary experiments are consistent with a mechanism involving dissociation of

  已开发出铱催化的苄胺的芳烃CH硼氢化反应，可转化典型的空间控制产物分布，从而提供邻位取代的硼酸酯。发现吡啶甲基胺是取代4,4'-二叔丁基联吡啶的理想配体，以诱导导向作用。初步实验与涉及半不稳定二胺配体的一种胺解离的机理是一致的。
• Synthesis of Biaryl Ethers by the Copper-Catalyzed Chan–Evans–Lam Etherification from Benzylic Amine Boronate Esters
  作者：Justin S. Marcum、Kathryn A. McGarry、Carl J. Ferber、Timothy B. Clark

  DOI：10.1021/acs.joc.6b01254

  日期：2016.9.2

  benzylic amines with phenols has been achieved to provide biaryl ethers that are prevalent in biologically active compounds. A variety of substitution patterns on the aryl boronate ester and the phenol are tolerated under the reaction conditions, providing moderate to high yields. A competition reaction between phenol and aniline revealed condition-dependent selectivity in which the phenol could be highly

  已经实现了邻苯甲酰化苄基胺与苯酚的铜催化醚化，以提供在生物活性化合物中普遍存在的联芳醚。在反应条件下，可以耐受芳基硼酸酯和苯酚上的多种取代方式，从而提供中等至高收率。苯酚和苯胺之间的竞争反应显示了条件依赖性的选择性，其中苯酚可能比苯胺更受青睐。
• Role of Hemilabile Diamine Ligands in the Amine-Directed C–H Borylation of Arenes
  作者：Lillian V. A. Hale、Kathryn A. McGarry、Marissa A. Ringgold、Timothy B. Clark

  DOI：10.1021/om5007837

  日期：2015.1.12

  A study of the role played by the bidentate ligand used in amine-directed CH borylation is described. Both reaction conversion and selectivity were significantly impacted when steric congestion and electronic perturbations of the bidentate diamine ligand were made, but a more significant influence was imparted by reducing the bite angle of the ligand. N-Benzylaminopyridine was identified as a general ligand that improves both selectivity and yield for most problematic substrates previously reported with picolylamine as ligand.
• Selective Formation of <i>ortho</i>-Aminobenzylamines by the Copper-Catalyzed Amination of Benzylamine Boronate Esters
  作者：Kathryn A. McGarry、Alexi A. Duenas、Timothy B. Clark

  DOI：10.1021/acs.joc.5b01074

  日期：2015.7.17

  The copper-catalyzed coupling between benzylamino boronate esters and aryl amines has been investigated. Formation of ortho-aminobenzylamines was achieved under oxidative conditions in the presence of copper(II) acetate. The major side product of the transformation is the homocoupling of the aryl boronate ester. The formation of the desired diamines was found to be improved in the absence of base,

  已经研究了苄基氨基硼酸酯和芳基胺之间的铜催化偶联。邻位形成在乙酸铜（II）的存在下，在氧化条件下获得-氨基苄胺。转化的主要副产物是芳基硼酸酯的均偶联。发现在不存在碱的情况下所需二胺的形成得到改善，相对于均偶联产物增加了选择性。在反应条件下，在硼酸酯底物和苯胺偶联配偶体上都可以同时接受给电子和吸电子取代基。相邻苄胺基团的存在似乎增强了硼酸酯的反应性并影响了最终产物的分布，这可能是通过影响催化循环中金属转移的竞争速率来实现的。
• Rh-Catalyzed <i>Ortho</i>-Selective C–H Borylation of <i>N</i>-Functionalized Arenes with Silica-Supported Bridgehead Monophosphine Ligands
  作者：Soichiro Kawamorita、Tatsuya Miyazaki、Hirohisa Ohmiya、Tomohiro Iwai、Masaya Sawamura

  DOI：10.1021/ja208364a

  日期：2011.12.7

  Supported phosphine-Rh systems, prepared in situ from silica-supported bridgehead monophosphines and [Rh(OH)(cod)]2, have enabled ortho-selective C-H borylation for a range of arenes containing nitrogen-based directing groups. The regioselectivity was excellent with various N-directing groups, including saturated and unsaturated N-heterocycles, tert-aminoalkyl groups, and iminetype C-N double bonds. The reaction showed significant tolerance toward steric repulsion around the reacting C-H bond. This Rh catalysis complements the Jr-catalyzed orthoborylation, which is effective for arenes with oxygen-based directing groups.