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钌氧配合物介导的需氧烯烃环氧化反应中的水共催化作用。

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

作者信息

Cao Qun, Diefenbach Martin, Maguire Calum, Krewald Vera, Muldoon Mark J, Hintermair Ulrich

机构信息

School of Chemistry and Chemical Engineering, Queen's University Belfast Northern Ireland UK

Dynamic Reaction Monitoring Facility, Institute for Sustainability, University of Bath UK

出版信息

Chem Sci. 2024 Jan 9;15(9):3104-3115. doi: 10.1039/d3sc05516g. eCollection 2024 Feb 28.

DOI:10.1039/d3sc05516g
PMID:38425537
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10901482/
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 Ru di-oxo complex for alkene epoxidation hydrogen bonding, stabilises the Ru mono-oxo intermediate, and is involved in the regeneration of the Ru 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.

摘要

我们报道了一种通用的钌卟啉催化剂体系的开发，该体系在温和条件下可对芳香族和脂肪族（内）烯烃进行有氧环氧化反应，产物收率高达95%，周转数（TON）高达300。研究表明，水在该反应中起着关键作用，能显著提高催化剂效率并扩大底物范围。采用计算研究和一系列实验技术进行的详细机理研究表明，水通过氢键作用活化钌双氧配合物以进行烯烃环氧化反应，稳定单氧钌中间体，并参与导致氧原子交换的双氧钌配合物的再生过程。在有水存在的情况下获得了不同的动力学数据，并确定了与催化剂失活相关的副反应。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9a2e/10901482/cd7b63a4c1a1/d3sc05516g-f9.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9a2e/10901482/cd7b63a4c1a1/d3sc05516g-f9.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9a2e/10901482/b45aa3cc6874/d3sc05516g-f5.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9a2e/10901482/cd7b63a4c1a1/d3sc05516g-f9.jpg

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