silver(I) 2,2,4,4,5,5,7,7,8,8,10,10,10-tridecafluoro-3,6,9-trioxadecanoate | 1600503-79-4

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 英文名称: silver(I) 2,2,4,4,5,5,7,7,8,8,10,10,10-tridecafluoro-3,6,9-trioxadecanoate
• 英文别名: silver(I) perfluoro-3,6,9-trioxadecanoate；silver(I) 3,6,9-trioxaperfluorodecanoate；silver perfluoro-3,6,9-trioxadecanoate
• CAS: 1600503-79-4
• 化学式: Ag*C₇F₁₃O₅
• 分子量: 518.921
• InChiKey: UJUIXHQTCVYLMO-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.27
• 重原子数：
  26.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  67.82
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  Hoveyda-Grubbs catalyst second generation 、 silver(I) 2,2,4,4,5,5,7,7,8,8,10,10,10-tridecafluoro-3,6,9-trioxadecanoate 以 二氯甲烷 为溶剂， 反应 3.0h， 以72.8%的产率得到[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene](2-isopropoxybenzylidene)bis(perfluoro-3,6,9-trioxadecanoyloxy)ruthenium(IV)
  参考文献：
  名称：

  Heavy fluorous phosphine-free ruthenium catalysts for alkene metathesis

  摘要：

  Second generation Grubbs catalyst was modified stepwise with perfluoroalkylated isopropoxystyrene and two perfluoroalkanoate or perfluoropolyoxaalkanoate ligands to afford heavy fluorous phosphine-free ruthenium complexes, which displayed high activity in model ring-closing metathesis reactions. Surprisingly, substitution with linear perfluoropolyether chains led to the complexes of higher activity and fluorophilicity compared to perfluoroalkyl chains, while the use of branched perfluoropolyether ponytails resulted in significantly inferior activity probably due to increased steric hindrance around the active ruthenium centre. Similar reactivity pattern with slightly lower activity was observed for the second generation Hoveyda-Grubbs catalysts bearing perfluoroalkanoate or perfluoropolyoxaalkanoate groups and non-fluorinated isopropoxybenzylidene ligand. Depending on the reaction system, unactivated precatalysts can be recycled by heavy fluorous extraction with perfluoro(methylcyclohexane). (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2014.03.003
• 作为产物：
  描述：

  2,2-二氟-2-[1,1,2,2-四氟-2-[1,1,2,2-四氟-2-(三氟甲氧基)乙氧基]乙氧基]-乙酸 、 silver(l) oxide 以 丙酮 为溶剂， 反应 5.0h， 以79%的产率得到silver(I) 2,2,4,4,5,5,7,7,8,8,10,10,10-tridecafluoro-3,6,9-trioxadecanoate
  参考文献：
  名称：

  Heavy fluorous phosphine-free ruthenium catalysts for alkene metathesis

  摘要：

  Second generation Grubbs catalyst was modified stepwise with perfluoroalkylated isopropoxystyrene and two perfluoroalkanoate or perfluoropolyoxaalkanoate ligands to afford heavy fluorous phosphine-free ruthenium complexes, which displayed high activity in model ring-closing metathesis reactions. Surprisingly, substitution with linear perfluoropolyether chains led to the complexes of higher activity and fluorophilicity compared to perfluoroalkyl chains, while the use of branched perfluoropolyether ponytails resulted in significantly inferior activity probably due to increased steric hindrance around the active ruthenium centre. Similar reactivity pattern with slightly lower activity was observed for the second generation Hoveyda-Grubbs catalysts bearing perfluoroalkanoate or perfluoropolyoxaalkanoate groups and non-fluorinated isopropoxybenzylidene ligand. Depending on the reaction system, unactivated precatalysts can be recycled by heavy fluorous extraction with perfluoro(methylcyclohexane). (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2014.03.003

文献信息

• Synthesis, catalytic activity and medium fluorous recycle of fluorous analogues of PEPPSI catalysts
  作者：Ondřej Šimůnek、Markéta Rybáčková、Martin Svoboda、Jaroslav Kvíčala

  DOI：10.1016/j.jfluchem.2020.109588

  日期：2020.8

  Comparison of catalytic activity of commercial catalysts with the modified ones in Suzuki-Miyaura cross-coupling reactions showed that the fluorous modifications mostly resulted in the increase of catalytic activity. Moreover, polyfluoroalkylation enabled efficient medium fluorous recycle of the modified catalysts using a two phase aqueous DMF/HFE 7500 ether system.

  PEPPSI配合物是空气和水分稳定的Pd催化剂，可方便地用于许多偶联反应中。为了获得可通过氟分离方法回收的Pd催化剂，我们通过在不同位置进行全氟烷基化或多氟烷基化改性了商用PEPPSI配合物的结构。修饰包括在NHC配体上使用线性多氟烷基代替一个芳基，吡啶配体的全氟烷基化，以及在Pd上用全氟链烷酸酯或全氟聚氧杂链烷酸酯取代氯配体。在铃木-宫浦的交叉偶联反应中，工业催化剂与改性催化剂的催化活性比较表明，氟的改性主要导致催化活性的增加。此外，
• Synthesis of Heavy Fluorous Ruthenium Metathesis Catalysts Using the Stereoselective Addition of Polyfluoroalkyllithium to Sterically Hindered Diimines
  作者：Jan Hošek、Markéta Rybáčková、Jan Čejka、Josef Cvačka、Jaroslav Kvíčala

  DOI：10.1021/acs.organomet.5b00325

  日期：2015.7.13

  The stereoselective addition of 2-(perfluorohexyl)ethyllithium to moderately hindered diimines led to racemic diamines, which were further transformed to light or heavy fluorous analogues of Hoveyda-Grubbs second-generation precatalysts. The complex bearing the NHC ligand modified with four polyfluoroalkyl ponytails represents the first known example of an alkene metathesis precatalyst retaining its heavy fluorous properties in the active catalytic form. The synthesized complexes match the activity and stability of a commercial Hoveyda-Grubbs second-generation precatalyst in model RCM reactions forming iii- and tetrasubstituted double bonds. The fluorophilic catalyst was successfully recycled using heavy fluorous separation techniques.