Issue 9, 2024

Water co-catalysis in aerobic olefin epoxidation mediated by ruthenium oxo complexes

Abstract

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 RuVI di-oxo complex for alkene epoxidation via hydrogen bonding, stabilises the RuIV mono-oxo intermediate, and is involved in the regeneration of the RuVI 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.

Graphical abstract: Water co-catalysis in aerobic olefin epoxidation mediated by ruthenium oxo complexes

Supplementary files

Article information

Article type
Edge Article
Submitted
17 окт 2023
Accepted
05 янв 2024
First published
09 янв 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 3104-3115

Water co-catalysis in aerobic olefin epoxidation mediated by ruthenium oxo complexes

Q. Cao, M. Diefenbach, C. Maguire, V. Krewald, M. J. Muldoon and U. Hintermair, Chem. Sci., 2024, 15, 3104 DOI: 10.1039/D3SC05516G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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