biostudies-literatureAnsmann NDeutsche ForschungsgemeinschaftDFGe202210132https://www.ebi.ac.uk/biostudies/studies/S-EPMC9828832biostudies-literatureUnknown61(44)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.Angewandte Chemie (International ed. in English)Silicon Catalyzed C-O Bond Ring Closing Metathesis of Polyethers.PMC9828832GR5007/2-1Ansmann NGreb LThorwart TfalseSilicon 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 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.2022-01-01T00:00:00Z2022 Nov2026-03-17T15:46:11.055Z2025-04-19T23:09:52.412ZS-EPMC98288323610668510.1002/anie.202210132