Silicon catalyzed C-O bond ring closing metathesis of polyethers

The Lewis superacid bis(perchlorocatecholato)silane catalyzes C−O bond metathesis of alkyl ethers with an efficiency outperforming all earlier reported systems. Chemoselective ring contractions of macrocyclic crown ethers enable substrate-specific transformations, and an unprecedented ring-closing m...

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Hauptverfasser: Ansmann, Nils (VerfasserIn) , Thorwart, Thaddäus (VerfasserIn) , Greb, Lutz (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: [November 2, 2022]
In: Angewandte Chemie. International edition
Year: 2022, Jahrgang: 61, Heft: 44, Pages: 1-5
ISSN:1521-3773
DOI:10.1002/anie.202210132
Online-Zugang:Verlag, kostenfrei, Volltext: https://doi.org/10.1002/anie.202210132
Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202210132
Volltext
Verfasserangaben:Nils Ansmann, Thaddäus Thorwart, and Lutz Greb

MARC

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520 |a The Lewis superacid bis(perchlorocatecholato)silane catalyzes C−O bond metathesis of alkyl ethers with an efficiency outperforming all earlier reported systems. Chemoselective ring contractions of macrocyclic crown ethers enable substrate-specific transformations, and an unprecedented ring-closing metathesis of polyethylene glycols allows polymer-selective degradation. Quantum chemical computations scrutinize a high Lewis acidity paired with a simultaneous low propensity for polydentate substrate binding as critical for successful catalysis. Based on these mechanistic insights, a second-generation class of silicon Lewis superacid with enhanced efficacy is identified and demonstrated. 
650 4 |a Lewis Superacid 
650 4 |a Organosilanes 
650 4 |a Polyethylene Glycol 
650 4 |a Reaction Mechanism 
650 4 |a Ring Closing Metathesis 
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