A Cocatalyst Strategy to Enhance Ruthenium‐Mediated Metathesis Reactivity towards Electron‐Deficient Substrates

Ruthenium‐mediated olefin metathesis has been widely applied for the synthesis of various organic molecules and polymers. Inspired by the cocatalyst strategy for olefin polymerization, here we demonstrate that the ion of a chloride ion from various commercially available ruthenium catalysts signific...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2022-07, Vol.61 (29), p.e202203796-n/a
Main Authors: Si, Guifu, Tan, Chen, Chen, Min, Chen, Changle
Format: Article
Language:English
Subjects:
Alkenes
Catalysis
Catalysts
Chemical synthesis
Chloride ions
Closed-Loop Recycling
Cocatalyst
Copolymerization
Electrons
Material properties
Metathesis
Organic chemistry
Polyethylene
Polyethylenes
Polymerization
Polymers
Polyolefins
Ruthenium
Substrates
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Summary:Ruthenium‐mediated olefin metathesis has been widely applied for the synthesis of various organic molecules and polymers. Inspired by the cocatalyst strategy for olefin polymerization, here we demonstrate that the ion of a chloride ion from various commercially available ruthenium catalysts significantly enhances their reactivity towards electron‐deficient internal olefins. This cocatalyst strategy can be implemented in ethenolysis and cross‐metathesis reactions of FG‐CH=CH‐FG type substrates bearing electron‐withdrawing groups and the synthesis of telechelic polymers that can be converted to polyethylene‐like materials with closed‐loop recycling properties. The copolymerization of cyclic substrate with cycloolefins followed by hydrogenation afforded polyolefin materials with in‐chain break points. Interestingly, switchable catalysis was achieved in the absence and presence of a cocatalyst, which allowed the polymer microstructure and material properties to be fine‐tuned. The ion of a chloride ion from various commercially available ruthenium catalysts significantly enhances their reactivity towards electron‐deficient internal olefins. This cocatalyst strategy can be implemented in ethenolysis and cross‐metathesis reactions, as well as the synthesis of polyethylene‐like materials with closed‐loop recycling properties.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202203796