potassium 2,4,6-triphenylbenzenethiolate | 1364319-47-0

• 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: potassium 2,4,6-triphenylbenzenethiolate
• 英文别名: Potassium;2,4,6-triphenylbenzenethiolate
• CAS: 1364319-47-0
• 化学式: C₂₄H₁₇S*K
• 分子量: 376.563
• InChiKey: MIJQVUPXAZEFBY-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  potassium 2,4,6-triphenylbenzenethiolate 、 dichloro(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylylidene)(benzylidene)bis(pyridine)ruthenium(II) 以 四氢呋喃 为溶剂， 反应 3.0h， 以29%的产率得到
  参考文献：
  名称：

  Z选择性烯烃复分解反应的吡啶稳定的快速引发单硫醇钌催化剂

  摘要：

  与基于稳定的亚苄基醚配体的先前版本相比，作为稳定的供体配体的吡啶可显着提高单硫醇钌钌催化剂在烯烃复分解中的性能。新的吡啶稳定化钌烷基亚烷基在室温下仅需几分钟后，即可快速引发并达到可观的收率，并具有中等至高的Z选择性，可在终端烯烃的自我复分解中进行。而且，它们可以与包括酸在内的多种底物一起使用，并促进ω-链烯酸的自我复分解。吡啶稳定的单硫醇钌钌催化剂在大环闭环复分解反应的高底物稀释度和催化过程中能抵抗100°C以上的高温下也很有效。

  DOI：

  10.1021/acs.organomet.7b00441
• 作为产物：
  描述：

  2,4,6-三苯基苯硫酚 在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以83%的产率得到potassium 2,4,6-triphenylbenzenethiolate
  参考文献：
  名称：

  Theory-assisted development of a robust and Z-selective olefin metathesis catalyst

  摘要：

  理论和实验之间紧密的相互作用导致了一种新的、高度选择性的基于钌的烯烃转化催化剂的开发，该催化剂可以在空气中使用，使用未经纯化和未经脱气的底物和溶剂，并且可以在酸的存在下使用。

  DOI：

  10.1039/c4dt00409d

文献信息

• <i>Z</i>-Selective Monothiolate Ruthenium Indenylidene Olefin Metathesis Catalysts
  作者：Wietse Smit、Jonas B. Ekeli、Giovanni Occhipinti、Bartosz Woźniak、Karl W. Törnroos、Vidar R. Jensen

  DOI：10.1021/acs.organomet.9b00641

  日期：2020.2.10

  synthesizing and testing the first two such complexes (5a and 5b) bearing 3-phenylindenylidene, a ligand known to promote stability in other ruthenium-based olefin metathesis catalysts. The steric pressure resulting from the three bulky ligands (the NHC, the arylthiolate, and the indenylidene) forces the thiolate ligand to position itself trans to the NHC ligand, a configuration different from that of

  带有空间要求的芳基硫醇盐配体（SAr）的Ru-亚烷基构成在1-烯烃的复分解中Z-选择性的仅两类催化剂之一。特别令人感兴趣的是带有吡啶作为稳定供体配体的配合物，[RuCl（SAr）（= CHR）（NHC）（py）]（R =苯基或2-噻吩基，NHC = N-杂环卡宾，py =吡啶），在室温下几分钟内即可迅速引发催化并产生可观的收率，并具有中等至高的Z选择性。在这里，我们通过合成和测试前两个这样的配合物（5a和5b）带有3-苯基茚基，这是一种已知在其他钌基烯烃复分解催化剂中可提高稳定性的配体。由三个庞大的配体（NHC，芳基硫醇盐和茚基亚烷基）产生的空间压力迫使硫醇盐配体将自身反式定位为NHC配体，其构型与相应的亚烷基不同。出人意料的是，尽管这种构型与Z-选择性不相容并且减慢了吡啶的离解，但两种新的络合物在室温下容易引发。尽管它们的热稳定性低于典型的带有茚基的催化剂，但5a和5b在催化中相当稳定（
• [EN] IMPROVED OLEFIN METATHESIS CATALYSTS<br/>[FR] CATALYSEURS DE MÉTATHÈSE D'OLÉFINES AMÉLIORÉS
  申请人：BERGEN TEKNOLOGIOVERFØRING AS

  公开号：WO2017009232A1

  公开（公告）日：2017-01-19

  The present invention refers to novel ruthenium-based catalysts for olefin metathesis reactions, particularly to fast initiating catalysts having stereoselective properties. In olefin metathesis reactions, the disclosed catalysts provide a high catalytic activity combined with the capability to generate higher yields of the olefin metathesis product.

  本发明涉及新型基于钌的烯烃转化反应催化剂，特别是具有立体选择性特性的快速启动催化剂。在烯烃转化反应中，所公开的催化剂具有高催化活性，同时具备产生更高产率的烯烃转化产物的能力。
• NOVEL ORGANOMETALLIC CATALYSTS
  申请人：Bergen Teknologioverforing AS

  公开号：US20150025212A1

  公开（公告）日：2015-01-22

  The present invention refers to novel ruthenium- and osmium-based catalysts for olefin metathesis reactions, particularly to catalysts having stereoselective properties. Z-selectivity is obtained by utilising two mono-anionic ligands of very different steric requirement. In olefin metathesis reactions these catalysts selectively provide the Z-isomer of disubstituted olefinic products even in presence of air or of acids.

  本发明涉及新型的铼和锇基催化剂，用于烯烃交换反应，特别是具有立体选择性的催化剂。通过利用两个单阴离子配体的非常不同的立体要求，可以获得Z-选择性。在烯烃交换反应中，即使存在空气或酸，这些催化剂也可以选择性地提供二取代烯烃产物的Z异构体。
• Ruthenium and Osmium Heterocyclic Carbene Metathesis Catalysts
  申请人：Bergen Teknologioverføring AS

  公开号：EP2826783B1

  公开（公告）日：2016-04-27
• Phosphine-Based <i>Z</i>-Selective Ruthenium Olefin Metathesis Catalysts
  作者：Wietse Smit、Vitali Koudriavtsev、Giovanni Occhipinti、Karl W. Törnroos、Vidar R. Jensen

  DOI：10.1021/acs.organomet.6b00214

  日期：2016.6.13

  Whereas a number of highly Z-selective ruthenium-based olefin metathesis catalysts bearing N-heterocyclic carbene ligands have been, reported in recent years, Z-selectivity has so far been difficult to achieve for phosphine-based catalysts. Guided :by predictive density functional theory (DFT) calculations, we have developed phosphine-based ruthenium olefin metathesis catalysts giving 70-95% of the Z-isomer product in homocoupling of terminal alkenes such as allylbenzene; 1-octene, alkyl acetate, and 2-allyloxyethanol. Starting from a moderately selective catalyst, [P(Cy)(3)] (-S-2,4,6-Ph-C6H2)ClRu(=CH-o-(OPrC6H4)-Pr-i) (4, Cy = cyclohexyl, Pr-i = isopropyl); obtained by substituting a chloride of the Hoveyda-Grubbs first-generation catalyst with 2,4,6-triphenylbenzenethiolate, we moved, on to replace Cl and PCy3 by chelating, anionic phosphine ligands. Such ligands increase selectivity by limiting rotation around the P-Ru bond and by specifically directing the steric bulk of the phosphine substituents toward the selectivity-inducing thiolate ligand. In particular, OFT calculations predicted that o-(dialkylphosphino)phenolate ligands should improve selectivity and activity compared to 4. The most promising of these conapounds (8b); based on the o-(ditert-butylphosphino)phenolate ligand, directs-the two P-bonded tert-butyl substituents toward the 2,4,6-triphenylbenzenethiolate and has little steric hindrance trans to the thiolate. This compound metathesizes terminal olefins such as allylbenzene and 1-octene with 2-selectivities above 80% and allylacetate above 90%. Although these phosphine-based ruthenium monothiolate catalysts in general achieve somewhat lower activities and Z-selectivities than their second-generation counterparts, they also offer examples giving less substrate and product isomerization and thus higher yields.