Water co-catalysis in aerobic olefin epoxidation mediated by ruthenium oxo complexes.
| Autor: | Cao Q; School of Chemistry and Chemical Engineering, Queen's University Belfast Northern Ireland UK m.j.muldoon@qub.ac.uk.; Dynamic Reaction Monitoring Facility, Institute for Sustainability, University of Bath UK u.hintermair@bath.ac.uk., Diefenbach M; Theoretical Chemistry, Department of Chemistry, Technische Universität Darmstadt Germany krewald@chemie.tu-darmstadt.de., Maguire C; School of Chemistry and Chemical Engineering, Queen's University Belfast Northern Ireland UK m.j.muldoon@qub.ac.uk., Krewald V; Theoretical Chemistry, Department of Chemistry, Technische Universität Darmstadt Germany krewald@chemie.tu-darmstadt.de., Muldoon MJ; School of Chemistry and Chemical Engineering, Queen's University Belfast Northern Ireland UK m.j.muldoon@qub.ac.uk., Hintermair U; Dynamic Reaction Monitoring Facility, Institute for Sustainability, University of Bath UK u.hintermair@bath.ac.uk. |
|---|---|
| Jazyk: | angličtina |
| Zdroj: | Chemical science [Chem Sci] 2024 Jan 09; Vol. 15 (9), pp. 3104-3115. Date of Electronic Publication: 2024 Jan 09 (Print Publication: 2024). |
| DOI: | 10.1039/d3sc05516g |
| Abstrakt: | We report the development of a versatile Ru-porphyrin catalyst system which performs the aerobic epoxidation of aromatic and aliphatic (internal) alkenes under mild conditions, with product yields of up to 95% and turnover numbers (TON) up to 300. Water is shown to play a crucial role in the reaction, significantly increasing catalyst efficiency and substrate scope. Detailed mechanistic investigations employing both computational studies and a range of experimental techniques revealed that water activates the Ru VI di-oxo complex for alkene epoxidation via hydrogen bonding, stabilises the Ru IV mono-oxo intermediate, and is involved in the regeneration of the Ru VI di-oxo complex leading to oxygen atom exchange. Distinct kinetics are obtained in the presence of water, and side reactions involved in catalyst deactivation have been identified. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.) |
| Databáze: | MEDLINE |
| Externí odkaz: |
|