A Fast-Initiating Ionically Tagged Ruthenium Complex: A Robust Supported Pre-catalyst for Batch-Process and Continuous-Flow Olefin Metathesis

被引:41
作者
Borre, Etienne [2 ]
Rouen, Mathieu [2 ]
Laurent, Isabelle [2 ]
Magrez, Magaly [2 ]
Caijo, Frederic [2 ]
Crevisy, Christophe [2 ]
Solodenko, Wladimir [1 ]
Toupet, Loic [3 ]
Frankfurter, Rene [4 ]
Vogt, Carla [4 ]
Kirschning, Andreas [1 ]
Mauduit, Marc [2 ]
机构
[1] Leibniz Univ Hannover, Inst Organ Chem, D-30167 Hannover, Germany
[2] Ecole Natl Super Chim Rennes, CNRS, UMR 6226, F-35708 Rennes 7, France
[3] Univ Rennes 1, Inst Phys Rennes, CNRS, UMR 6251, F-35042 Rennes, France
[4] Leibniz Univ Hannover, Inst Anorgan Chem, D-30167 Hannover, Germany
关键词
flow reactors; immobilization; olefin metathesis; ruthenium; supported catalysts; RING-CLOSING METATHESIS; 2ND-GENERATION HOVEYDA-GRUBBS; HETEROCYCLIC CARBENE LIGANDS; RECYCLABLE CATALYST; EFFICIENT CATALYSTS; ORGANIC-SYNTHESIS; CONVENIENT METHOD; MECHANISM; DESIGN; MICROREACTORS;
D O I
10.1002/chem.201201589
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In this study, a new pyridinium-tagged Ru complex was designed and anchored onto sulfonated silica, thereby forming a robust and highly active supported olefin-metathesis pre-catalyst for applications under batch and continuous-flow conditions. The involvement of an oxazinebenzylidene ligand allowed the reactivity of the formed Ru pre-catalyst to be efficiently controlled through both steric and electronic activation. The oxazine scaffold facilitated the introduction of the pyridinium tag, thereby affording the corresponding cationic pre-catalyst in good yield. Excellent activities in ring-closing (RCM), cross (CM), and enyne metathesis were observed with only 0.5 mol?% loading of the pre-catalyst. When this powerful pre-catalyst was immobilized onto a silica-based cationic-exchange resin, a versatile catalytically active material for batch reactions was generated that also served as fixed-bed material for flow reactors. This system could be reused at 1 mol?% loading to afford metathesis products in high purity with very low ruthenium contamination under batch conditions (below 5 ppm). Scavenging procedures for both batch and flow processes were conducted, which led to a lowering of the ruthenium content to as little as one tenth of the original values.
引用
收藏
页码:16369 / 16382
页数:14
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