Silicon catalyzed C-O bond ring closing metathesis of polyethers

• Verfasst von: Ansmann, Nils [VerfasserIn]
• Verfasst von: Thorwart, Thaddäus [VerfasserIn]
• Verfasst von: Greb, Lutz [VerfasserIn]
• Titel: Silicon catalyzed C-O bond ring closing metathesis of polyethers
• Verf.angabe: Nils Ansmann, Thaddäus Thorwart, and Lutz Greb
• E-Jahr: 2022
• Jahr: [November 2, 2022]
• Umfang: 5 S.
• Illustrationen: Illustrationen
• Fussnoten: First published: 15 September 2022 ; Gesehen am 20.12.2022
• Titel Quelle: Enthalten in: Angewandte Chemie / International edition
• Ort Quelle: Weinheim : Wiley-VCH, 1962
• Jahr Quelle: 2022
• Band/Heft Quelle: 61(2022), 44 vom: Sept., Artikel-ID e202210132, Seite 1-5
• ISSN Quelle: 1521-3773
• DOI: doi:10.1002/anie.202210132
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: Lewis Superacid
• Sach-SW: Organosilanes
• Sach-SW: Polyethylene Glycol
• Sach-SW: Reaction Mechanism
• Sach-SW: Ring Closing Metathesis
• K10plus-PPN: 1828123641

Abstract

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.