1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,5-dimethyl-1,2-dihydropyridine | 1345455-89-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,5-dimethyl-1,2-dihydropyridine
• 英文别名: 1-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-3,5-dimethyl-1,2-dihydropyridine；3,5-dimethyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2H-pyridine
• CAS: 1345455-89-1
• 化学式: C₁₃H₂₂BNO₂
• 分子量: 235.134
• InChiKey: MAJYCLSAEQEBBJ-UHFFFAOYSA-N

物化性质

• 沸点：
  261.0±33.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.74
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 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：

  N-甲基马来酰亚胺 、 1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,5-dimethyl-1,2-dihydropyridine 以 氘代苯 为溶剂， 反应 24.0h， 生成 8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4,11-trimethyl-4,8-diazatricyclo[5.2.2.0(2,6)]undec-10-ene-3,5-dione
  参考文献：
  名称：

  吡啶的铑催化硼氢化反应区域选择性合成1,2-二氢吡啶

  摘要：

  在铑催化剂的存在下，吡啶在 50 °C 下加入频哪醇硼烷，以高产率得到 N-boryl-1,2-dihydropyridine。选择性的 1,2-硼氢化反应也发生在取代吡啶的反应中。在3-取代吡啶的反应中，3-取代的N-boryl-1,2-二氢吡啶区域选择性地形成。

  DOI：

  10.1021/ja3002953
• 作为产物：
  描述：

  3,5-二甲基吡啶 、 频那醇硼烷 在 [Cp*(Ph₂PC₆H₄S)Fe]₂(μ-N₂) 作用下， 以 氘代苯 为溶剂， 反应 24.0h， 以61%的产率得到1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,5-dimethyl-1,2-dihydropyridine
  参考文献：
  名称：

  N-杂芳烃的铁催化1,2-选择性硼氢化反应

  摘要：

  已发现 N2 桥连二铁络合物 [Cp*(Ph2PC6H4S)Fe]2(μ-N2) (1) 可催化 N-杂芳烃与频哪醇硼烷的硼氢化反应，得到具有高区域选择性的 N-硼化 1,2-还原产物. 催化是通过 N-杂芳烃与铁中心的配位引发的，而 BH 键裂解是速率决定步骤。

  DOI：

  10.1021/jacs.7b11416

文献信息

• Atom-efficient regioselective 1,2-dearomatization of functionalized pyridines by an earth-abundant organolanthanide catalyst
  作者：Alexander S. Dudnik、Victoria L. Weidner、Alessandro Motta、Massimiliano Delferro、Tobin J. Marks

  DOI：10.1038/nchem.2087

  日期：2014.12

  synthesis. Dearomatization of pyridine derivatives is an important transformation to access a wide range of valuable nitrogenous natural products, pharmaceuticals and materials. Here, we report an efficient 1,2-regioselective organolanthanide-catalysed pyridine dearomatization process using pinacolborane, which is compatible with a broad range of pyridines and functional groups and employs equimolar

  开发用于高价值化学转化的地球上丰富的非铂金属催化剂是当代化学合成的关键挑战。吡啶衍生物的脱芳香化反应是一种重要的转化方法，可用于获得各种有价值的含氮天然产物，药物和材料。在这里，我们报告使用频哪醇硼烷的有效的1,2-区域选择性有机镧系元素催化的吡啶脱芳香化过程，该化合物与广泛的吡啶和官能团兼容，并采用等摩尔试剂化学计量。关于机理，由NMR光谱和动力学测量得出的速率定律表明催化剂浓度为一级，吡啶浓度为分数级，而频哪醇硼烷浓度为反一级，C = N插入到La–H键中作为营业额的确定。高能跨度分析提供了对实验活性趋势和异常动力学行为的更详细了解，并提出了催化剂的“静止”状态和潜在的失活途径。
• Regioselective 1,2-Dearomatization of Functionalized Azines by Organolanthanide Catalysts
  申请人：Northwestern University

  公开号：US20160159825A1

  公开（公告）日：2016-06-09

  A 1,2-regioselective organolanthanide-catalyzed azine dearomatization process using pinacolborane is disclosed.

  揭示了一种使用缔合硼酸钙催化的1,2-区域选择性芳香烃脱芳构化过程。
• Magnesium-Catalyzed Hydroboration of Pyridines
  作者：Merle Arrowsmith、Michael S. Hill、Terrance Hadlington、Gabriele Kociok-Köhn、Catherine Weetman

  DOI：10.1021/om2008138

  日期：2011.11.14

  Reaction of catalytic quantities of a beta-diketiminato n-butylmagnesium complex with pinacol-borane in the presence of pyridine derivatives provides facile access to borylated dihydropyridines. The reaction is applicable to a wide range of monocyclic and fused-ring pyridine derivatives and catalytic turnover is proposed to occur through a well-defined sequence of Mg-H/pyridine dearomatization and Mg-N/B-H sigma bond metathesis steps.
• Cerium-Hydride Secondary Building Units in a Porous Metal–Organic Framework for Catalytic Hydroboration and Hydrophosphination
  作者：Pengfei Ji、Takahiro Sawano、Zekai Lin、Ania Urban、Dean Boures、Wenbin Lin

  DOI：10.1021/jacs.6b10055

  日期：2016.11.16

  We report the stepwise, quantitative transformation of Ce-6(IV)(mu(3)-O)(4)(mu(3)-OH)(4)(OH)(6)(OH2)(6) nodes in a new Ce-BTC (BTC = trimesic acid) metal-organic framework (MOF) into the first Ce-6(III)(mu(3)-O)(4)(mu(3)-OLi)(4)(H)(6)(THF)(6)Li-6 metal-hydride nodes that effectively catalyze hydroboration and hydrophosphination reactions. CeH-BTC displays low steric hindrance and electron density compared to homogeneous organolanthanide catalysts, which likely accounts for the unique 1,4-regioselectivity for the hydroboration of pyridine derivatives. MOF nodes can thus be directly transformed into novel single-site solid catalysts without homogeneous counterparts for sustainable chemical synthesis.
• Multinuclear Magnesium Hydride Clusters: Selective Reduction and Catalytic Hydroboration of Pyridines
  作者：Julia Intemann、Martin Lutz、Sjoerd Harder

  DOI：10.1021/om500469h

  日期：2014.10.27

  Multinuclear magnesium hydride complexes react with pyridine, forming 1,2- and 1,4-dihydropyridide (DHP) complexes. Reaction of PARA(3)Mg(8)H(10) with pyridine initially formed 1,2-DHP and 1,4-DHP product mixtures which converted at 60 degrees C into PARA-[Mg(1,4-DHP)]2.(pyridine)2 (PARA = [(2,6-iPr2C6H3)NC(Me)C(H)C(Me)N]2-(p-C6H4)). Reaction of [NN-(MgH)(2)](2) with pyridine gave exclusive formation of the 1,2-DHP product NN-[Mg(1,2-DHP)](2).(pyridine)2 (NN = [(2,6-iPr(2)C(6)H(3))NC(Me)CHC(Me)N-](2)). Both products were characterized by crystal structure determinations. The unusual preference for 1,2-addition is likely caused by secondary intramolecular interactions based on mutual communication between the metal coordination geometries: an extended network of CH...C p-interactions and p-stacking interactions is found. Whereas PARA3Mg(8)H(10) is hardly active in magnesium-catalyzed hydroboration of pyridines with pinacolborane, [NN-(MgH)(2)](2) shows efficient coupling. However, the regioselectivity of the stoichiometric reaction is not translated to the catalytic regime. This result is taken as an indication for a potential alternative mechanism in which magnesium hydride intermediates do not play a role but the hydride is transferred from an intermediate borate complex.