N-(2-(3-mesityl-2,3-dihydro-1H-imidazol-1-yl)ethyl)-2-methylpropan-2-amine | 934371-69-4

• 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: N-(2-(3-mesityl-2,3-dihydro-1H-imidazol-1-yl)ethyl)-2-methylpropan-2-amine
• 英文别名: (t-butyl)NHCH2CH2C3H2N2(mesityl)；C3H2N2(Mes)(CH2CH2NHtBu)；(C((N-mesityl)N(CHCH)N(CHCH2NH-t-Bu)))；2-methyl-N-[2-[3-(2,4,6-trimethylphenyl)-2H-imidazol-1-ium-2-id-1-yl]ethyl]propan-2-amine
• CAS: 934371-69-4
• 化学式: C₁₈H₂₇N₃
• 分子量: 285.432
• InChiKey: ILTLGWBKONKCCC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  18.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(2-(3-mesityl-2,3-dihydro-1H-imidazol-1-yl)ethyl)-2-methylpropan-2-amine 以 四氢呋喃 、 乙醚 为溶剂， 反应 10.0h， 生成 Ph3B(C((N-mesityl)N(CHCH)N(CHCH2N(t-Bu)C(O)NH-C6H4Me))
  参考文献：
  名称：

  Subtle Reactivities of Boron and Aluminum Complexes with Amino-Linked N-Heterocyclic Carbene Ligation

  摘要：

  This paper describes the synthesis and characterization of trimethylaluminum (2a), dimethylaluminum (3a), and triphenylboron complexes (7) supported by functional amine-linked NHC ligands. The chemical reactivity studies with carbodiimide and isocyanate were preformed with 2a and 3a, illustrating the noninnocent nature in Al-carbene bonding. However, the boron-carbene interaction is quite robust against addition of these substrates even at higher temperature conditions. The subtle difference in chemical reactivity between aluminum and boron is attributed from the metal-carbene bond covalency. Development of the catalytic method for Suzuki-Miyaura coupling utilizing triphenylboron reagent supported by amino-NHC is also presented.

  DOI：

  10.1021/om200878e
• 作为试剂：
  描述：

  2-环己烯-1-酮 、 联硼酸频那醇酯 在 N-(2-(3-mesityl-2,3-dihydro-1H-imidazol-1-yl)ethyl)-2-methylpropan-2-amine 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以82%的产率得到环己酮-3-硼酸酯
  参考文献：
  名称：

  胺连接的N-杂环卡宾：侧链游离胺助剂在催化反应中的重要性

  摘要：

  我们已经成功地扩展了胺基上具有不同取代基的氨基-NHC库，从而使人们对悬空的胺侧臂之间的分子间相互作用引起的NHC不稳定性有了更深入的了解。然而，侧链胺在催化过程中起着重要作用，通过仲胺引起的协同作用来恢复不饱和NHC的催化活性。这一概念证明使我们能够将催化范围扩展到C CC以及CB键的形成。

  DOI：

  10.1002/asia.201000829

文献信息

• Mechanistic Study of a Switch in the Regioselectivity of Hydroheteroarylation of Styrene Catalyzed by Bimetallic Ni-Al through CH Activation
  作者：Wen-Ching Chen、Ying-Chieh Lai、Wei-Chun Shih、Ming-Shiuan Yu、Glenn P. A. Yap、Tiow-Gan Ong

  DOI：10.1002/chem.201400303

  日期：2014.6.23

  previously reported a highly efficient protocol for bimetallic Ni–Al‐catalyzed hydroheteroarylation of styrene with benzimidazole based on CH bond activation. We have now delineated the mechanism of this process, providing a rationale for an observed switch in regioselectivity in the presence of the Lewis acid, AlMe3. The present mechanistic study gives insights for the rational development of catalysts

  我们以前报道为苯乙烯与苯并咪唑基于C的双金属镍-铝催化hydroheteroarylation一个高效的协议 H键活化。现在，我们描述了该过程的机制，为在路易斯酸AlMe 3存在下观察到的区域选择性转换提供了理论依据。目前的机理研究为合理开发具有所需线性/支化选择性的催化剂提供了见识。
• Two-Way Street Transformation of Boronium and Borane Complexes Facilitated by Amino-Linked N-Heterocyclic Carbene
  作者：Jie-Hong Tsai、Shen-Ta Lin、Richard Bing-Gong Yang、Glenn P. A. Yap、Tiow-Gan Ong

  DOI：10.1021/om100747j

  日期：2010.9.27

  We have obtained boronium complexes upon reaction of an amino-NHC lithium bromide adduct with borane. Unexpectedly, the treatment of the boronium complexes with silver triflate led to the isolation of a bis-borane compound containing two chemically different boron centers. The bis-borane and boronium complexes can interconvert via a four-membered intermediate metallacycle consisting of a three-center

  通过氨基-NHC溴化锂加合物与硼烷的反应，我们获得了硼配合物。出乎意料的是，用三氟甲磺酸银处理硼配合物导致分离出含有两个化学上不同的硼中心的双硼烷化合物。双硼烷和硼配合物可以通过四元中间金属环互变，该四元中间金属环由胺侧链辅助的三中心，两个电子的B-H-B键基序组成。
• Kinetic and Thermodynamic Study of <i>Syn−Anti</i> Isomerization of Nickel Complexes Bearing Amino-Linked N-Heterocyclic Carbene Ligands: The Effect of the Pendant Arm of the NHC
  作者：Yi-Ping Huang、Chung-Chih Tsai、Wei-Chih Shih、Yu-Chang Chang、Shen-Ta Lin、Glenn P. A. Yap、Ito Chao、Tiow-Gan Ong

  DOI：10.1021/om900404c

  日期：2009.8.10

  analysis and various spectroscopy and theoretical results, we have ruled out a cis−trans isomerization, but confirmed a syn-anti conformational equilibrium exhibited in the solution of 3. The variable-temperature NMR for complexes 3 are consistent with restricted rotation about the nickel−carbene carbon bond. Plots of Keq vs 1/T are obtained with calculated ΔH° of 6.03 and 7.61 kJ/mol and ΔS° of 16.1 and

  所述单- （2）和双（氨基- NHC）（3）卤化镍配合物可以以中等产率的Ni（PPH反应来制备3）2 X 2与氨基连接的侧链NHC 1，[C （MES）N （CHCH）N（CH 2 CH 2 NH t Bu）}]或其溴化锂卡宾加合物1-LiBr。单（氨基-卡宾）镍配合物（2）是带有四面体扭曲的Ni中心的顺磁性物质，其特征在于通过NHC和胺键合形成双齿配位模式。相反，双（氨基-卡宾）镍络合物（3）具有质子NMR活性，由具有两个反式NHC部分的正方形平面几何结构组成。配合物2和3都包含与文献价值相当的镍-卡宾键。在溶液结构中观察到3的两种形式的异构体产物，但是尽管使用不同极性的各种溶剂进行了许多尝试，但仅获得了固体结构的顺反异构体。根据粉末X射线分析和各种光谱学及理论结果，我们排除了顺反异构化，但确认3的溶液中存在顺反构象平衡。。配合物3的可变温度NMR与围绕镍-卡宾碳键的受限制的旋转一致。的曲线图ķ当量对1
• The Zirconium Benzyl Mediated C−N Bond Cleavage of an Amino-Linked N-Heterocyclic Carbene
  作者：Yu-Cheng Hu、Chung-Chih Tsai、Wei-Chih Shih、Glenn P. A. Yap、Tiow-Gan Ong

  DOI：10.1021/om900971c

  日期：2010.2.8

  We report a nonreductive process mediated by zirconium alkyl complexes for the C−H bond activation and C−N bond cleavage of an anionic amino-linked carbene at room temperature. Reacting the amino-linked NHC with Zr(Bz)4 led to the isolation of a rare species of metastable Zr complex possessing an azaallyl and an η2-N,C-imidazolyl carbene moiety.

  我们报道了在室温下，由锆烷基络合物介导的阴离子氨基连接卡宾的CH键活化和CN键裂解的非还原过程。反应用的Zr氨基联NHC（BZ）4导致复杂的具有一个azaallyl和η亚稳Zr的稀有物种的隔离2 - Ñ，Ç咪唑基碳烯部分。
• Bimetallic Nickel Aluminun Mediated <i>Para</i>-Selective Alkenylation of Pyridine: Direct Observation of η²,η¹-Pyridine Ni(0)−Al(III) Intermediates Prior to C−H Bond Activation
  作者：Chung-Chih Tsai、Wei-Chih Shih、Cyong-Hui Fang、Chia-Yi Li、Tiow-Gan Ong、Glenn P. A. Yap

  DOI：10.1021/ja1061246

  日期：2010.9.1

  We have presented new amino-NHC Ni-Al complex mediated para C-H bond activation for pyridine and quinolin, and isolated for the first time the intermediate structure of a bimetallic eta(2),eta(1)-pyridine pyridine nickel aluminum complex prior to its C-H activation, which serves as key evidence for bimetallic catalysis.