1-(2,6-diisopropylphenyl)-4,5-dimethyl-1H-imidazole | 647841-32-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1-(2,6-diisopropylphenyl)-4,5-dimethyl-1H-imidazole
• 英文别名: 1-[2,6-Di(propan-2-yl)phenyl]-4,5-dimethyl-1H-imidazole；1-[2,6-di(propan-2-yl)phenyl]-4,5-dimethylimidazole
• CAS: 647841-32-5
• 化学式: C₁₇H₂₄N₂
• 分子量: 256.391
• InChiKey: BMZHJLHDRNSILU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  17.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(2,6-diisopropylphenyl)-4,5-dimethyl-1H-imidazole 在 正丁基锂 、 potassium hydride 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， -78.0~80.0 ℃ 、101.33 kPa 条件下， 反应 75.17h， 生成 2-(1-(2,6-diisopropylphenyl)-3-isopropyl-4,5-dimethyl-1H-imidazol-3-ium-2-yl)acetate
  参考文献：
  名称：

  Fast CO₂ Sequestration, Activation, and Catalytic Transformation Using N-Heterocyclic Olefins

  摘要：

  N-Heterocyclic Olefin (NHO) with high electronegativity at the terminal carbon atom was found to show a strong tendency for CO2 sequestration, affording a CO2 adduct (NHO-CO2). X-ray single crystal analysis revealed the bent geometry of the binding CO2 in the NHO-CO2 adducts with an O-C-O angle of 127.7-129.9 degrees, dependent on the substitute groups of N-heterocyclic ring. The length of the C-carboxylate-C-NHO bond is in the range of 1.55-1.57 angstrom, significantly longer than that of the C-carboxylate-C-NHC bond (1.52-1.53 angstrom) of the previously reported NHC-CO2 adducts. The FTIR study by monitoring the v(CO2) region of transmittance change demonstrated that the decarboxylation of NHO-CO2 adducts is easier than that of the corresponding NHC-CO2 adducts. Notably, the NHO-CO2 adducts were found to be highly active in catalyzing the carboxylative cyclization of CO2 and propargylic alcohols at mild conditions (even at ambient temperature and 0.1 MPa CO2 pressure), selectively giving alpha-alkylidene cyclic carbonates in good yields. The catalytic activity is about 10-200 times that of the corresponding NHC-CO2 adducts at the same conditions. Two reaction paths regarding the hydrogen at the alkenyl position of cyclic carbonates coming from substrate (path A) or both substrate and catalyst (path B) were proposed on the basis of deuterium labeling experiments. The high activity of NHO-CO2 adduct was tentatively ascribed to its low stability for easily releasing the CO2 moiety and/or the desired product, a possible rate-limiting step in the catalytic cycle.

  DOI：

  10.1021/ja405114e
• 作为产物：
  描述：

  2,6-二异丙基苯胺 在 氯化铵 作用下， 以 甲醇 为溶剂， 反应 17.0h， 生成 1-(2,6-diisopropylphenyl)-4,5-dimethyl-1H-imidazole
  参考文献：
  名称：

  A Modified Procedure for the Synthesis of 1-Arylimidazoles

  摘要：

  提供了一种方便的改进过程，用于合成1-芳基取代的咪唑。该方法通常能获得空间位阻较大的1-芳基咪唑更高的产率。

  DOI：

  10.1055/s-2003-42444

文献信息

• Palladium‐Catalyzed Methylation of Nitroarenes with Methanol
  作者：Lin Wang、Helfried Neumann、Matthias Beller

  DOI：10.1002/anie.201814146

  日期：2019.4.8

  procedure for the synthesis of N‐methyl‐arylamines directly from nitroarenes using methanol as green methylating agent was developed. The key to success is the use of a specific catalyst system consisting of palladium acetate and the ligand 1‐[2,6‐bis(isopropyl)phenyl]‐2‐[tert‐butyl(2‐pyridinyl)phosphino]‐1H‐Imidazole (L1). The generality of this protocol is demonstrated in the synthesis of more than 20

  开发了使用甲醇作为绿色甲基化剂直接从硝基芳烃合成N-甲基-芳基胺的方法。成功的关键是使用由乙酸钯和配位体的1- [2,6-双（异丙基）苯基] -2- [叔-丁基（2-吡啶基）膦基] -1的特定催化剂体系的ħ -咪唑（L1）。在相对温和的条件下合成20多种N-甲基-芳基胺证明了该方案的普遍性。将这种新颖的方法与使用相同催化剂的后续偶联工艺相结合，可以使芳香族硝基化合物有效地分散为包括药物分子在内的各种胺类。
• Deuterodechlorination of Aryl/Heteroaryl Chlorides Catalyzed by a Palladium/Unsymmetrical NHC System
  作者：Masami Kuriyama、Norihisa Hamaguchi、Gemba Yano、Kotaro Tsukuda、Kanako Sato、Osamu Onomura

  DOI：10.1021/acs.joc.6b01609

  日期：2016.10.7

  The catalytic deuterodechlorination of aryl/heteroaryl chlorides was developed with a palladium/unsymmetrical NHC system, and the precisely controlled introduction of deuterium into a variety of aryl/heteroaryl compounds was achieved with a high level of efficiency, selectivity, and deuteration degree. This method was also successfully applied to the transformation of bioactive agents even in a gram-scale

  利用钯/不对称NHC体系开发了对芳基/杂芳基氯化物的催化氘代脱氯反应，并以高水平的效率，选择性和氘化度实现了将氘精确控制引入各种芳基/杂芳基化合物中的方法。即使在克级合成中，该方法也成功地应用于生物活性剂的转化。Pd-NHC配合物的晶体结构分析导致观察到Pd-芳烃相互作用。
• Nickel-Catalyzed Deoxygenative Deuteration of Aryl Sulfamates
  作者：Masami Kuriyama、Shota Kujirada、Kotaro Tsukuda、Osamu Onomura

  DOI：10.1002/adsc.201601105

  日期：2017.3.20

  The nickel‐catalyzed deoxygenative deuteration of aryl/heteroaryl sulfamates has been developed, and the effective incorporation of deuterium into a variety of aromatic compounds was achieved with sufficient catalytic efficiency and high deuteration degree. This process tolerated reducible functional moieties and heterocyclic structures. Additionally, a double introduction of deuterium also successfully

  已开发了镍催化的芳基/杂芳基氨基磺酸盐的脱氧氘代反应，并以足够的催化效率和较高的氘代度将氘有效地掺入了多种芳族化合物中。该过程容许可还原的功能部分和杂环结构。另外，两次引入氘也成功地获得了具有高产率和氘含量的所需产物。
• [EN] UNSYMMETRICAL N-HETEROCYCLIC CARBENE CATALYSTS AND METHODS USING SAME<br/>[FR] CATALYSEURS CARBÈNES N-HÉTÉROCYCLIQUES ASYMÉTRIQUES ET LEURS PROCÉDÉS D'UTILISATION
  申请人：UNIV RUTGERS

  公开号：WO2022187205A1

  公开（公告）日：2022-09-09

  The present disclosure relates in part to novel complexes of unsymmetrical N-heterocylic carbene (NHC) ligands and group 10 or 11 metals. The present disclosure further relates to methods of electrophilic functionalization of alkynes and/or nitriles using the NHC catalysts described herein.

  本公开涉及非对称N-杂环卡宾（NHC）配体和10或11族金属的新型配合物。本公开还涉及使用此处所描述的NHC催化剂进行炔烃和/或腈的亲电官能团化的方法。
• Wingtip‐Flexible <i>N</i>‐Heterocyclic Carbenes: Unsymmetrical Connection between IMes and IPr
  作者：Qun Zhao、Mahbubur Rahman、Tongliang Zhou、Shiyi Yang、Roger Lalancette、Roman Szostak、Michal Szostak

  DOI：10.1002/anie.202318703

  日期：2024.2.19

  IMes (IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene) and IPr (IPr=1,3‐ bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) represent by far the most frequently used N‐heterocyclic carbene ligands in homogeneous catalysis, however, despite numerous advantages, these ligands are limited by the lack of steric flexibility of catalytic pockets. We report a new class of unique unsymmetrical N‐heterocyclic carbene ligands that are characterized by freely‐rotatable N‐aromatic wingtips in the imidazol‐2‐ylidene architecture. The combination of rotatable N−CH₂Ar bond with conformationally‐fixed N−Ar linkage results in a highly modular ligand topology, entering the range of geometries inaccessible to IMes and IPr. These ligands are highly reactive in Cu(I)‐catalyzed β‐hydroboration, an archetypal borylcupration process that has had a transformative impact on the synthesis of boron‐containing compounds. The most reactive Cu(I)‐NHC in this class has been commercialized in collaboration with MilliporeSigma to enable broad access of the synthetic chemistry community. The ligands gradually cover %V_bur geometries ranging from 37.3 % to 52.7 %, with the latter representing the largest %V_bur described for an IPr analogue, while retaining full flexibility of N‐wingtip. Considering the modular access to novel geometrical space in N‐heterocyclic carbene catalysis, we anticipate that this concept will enable new opportunities in organic synthesis, drug discovery and stabilization of reactive metal centers.

  摘要IMes（IMes=1,3-双(2,4,6-三甲基苯基)咪唑-2-亚基）和 IPr（IPr=1,3-双(2,6-二异丙基苯基)咪唑-2-亚基）是迄今为止均相催化中最常用的 N-杂环碳烯配体，然而，尽管这些配体具有众多优点，但却因催化口袋缺乏立体灵活性而受到限制。我们报告了一类新的独特非对称 N-杂环碳烯配体，其特点是咪唑-2-亚基结构中的 N-芳香族翼尖可自由旋转。可旋转的 N-CH2Ar 键与构象固定的 N-Ar 连接相结合，形成了高度模块化的配体拓扑结构，进入了 IMes 和 IPr 无法访问的几何形状范围。这些配体在 Cu(I)催化的 β-硼氢化反应中具有很高的反应活性，这是一种典型的硼合过程，对含硼化合物的合成产生了变革性的影响。我们与 MilliporeSigma 公司合作，将该类反应活性最高的 Cu(I)-NHC 商品化，使合成化学界能够广泛使用。配体逐渐涵盖了从 37.3% 到 52.7% 的 %Vbur 几何结构，后者代表了 IPr 类似物中最大的 %Vbur，同时保留了 N 翼尖的充分灵活性。考虑到在 N-heterocyclic carbene 催化中模块化地进入新的几何空间，我们预计这一概念将为有机合成、药物发现和稳定活性金属中心带来新的机遇。