Silicon Catalyzed C−O Bond Ring Closing Metathesis of Polyethers

Journal article

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.

Authors: Ansmann, N; Thorwart, T; Greb, L

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: Wiley
• Journal: Angewandte Chemie International Edition
• Volume: 61
• Issue: 44
• Pages: e202210132-e202210132
• Publication date: 2022-09-15
• DOI: 10.1002/anie.202210132
• EISSN: 1521-3773
• ISSN: 1433-7851
• Language: English
• Keywords: Polymer; Silane; Substrate (aquarium); Salt metathesis reaction; Superacid; Chemistry; Lewis acids and bases; Combinatorial chemistry; Polymerization; Organic chemistry; Polymer chemistry; Catalysis; Metathesis; Ring-closing metathesis