1,2-Dichloro-4-hex-1-ynylbenzene | 1313370-90-9

• 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: 1,2-Dichloro-4-hex-1-ynylbenzene
• CAS: 1313370-90-9
• 化学式: C₁₂H₁₂Cl₂
• 分子量: 227.133
• InChiKey: CTHROWLKPBAXJL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,2-Dichloro-4-hex-1-ynylbenzene 、 a-叠氮基-苯乙酸甲酯 在 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以94%的产率得到methyl 2-butyl-3-(3,4-dichlorophenyl)-1-phenylcycloprop-2-enecarboxylate
  参考文献：
  名称：

  Silver Triflate-Catalyzed Cyclopropenation of Internal Alkynes with Donor-/Acceptor-Substituted Diazo Compounds

  摘要：

  Silver triflate was found to be an efficient catalyst for the cyclopropenation of internal alkynes using donor-/acceptor-substituted diazo compounds as carbenoid precursors. Highly substituted cyclopropenes, which cannot be synthesized directly via rhodium(II)-catalyzed carbenoid chemistry, can now be readily accessed.

  DOI：

  10.1021/ol201503j
• 作为产物：
  描述：

  3,4-二氯碘苯 、 1-己炔 在 bis-triphenylphosphine-palladium(II) chloride 、 三乙胺 、 copper(l) iodide 作用下， 反应 0.08h， 生成 1,2-Dichloro-4-hex-1-ynylbenzene
  参考文献：
  名称：

  Silver Triflate-Catalyzed Cyclopropenation of Internal Alkynes with Donor-/Acceptor-Substituted Diazo Compounds

  摘要：

  Silver triflate was found to be an efficient catalyst for the cyclopropenation of internal alkynes using donor-/acceptor-substituted diazo compounds as carbenoid precursors. Highly substituted cyclopropenes, which cannot be synthesized directly via rhodium(II)-catalyzed carbenoid chemistry, can now be readily accessed.

  DOI：

  10.1021/ol201503j

文献信息

• 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。