Abstract

Cycloruthenated complexes have been studied extensively over the last few decades. Many accounts of their synthesis, characterisation, and catalytic activity in a wide variety of transformations have been reported to date. Compared with their non-cyclometallated analogues, cycloruthenated complexes may display enhanced catalytic activities in known transformations or possess entirely new reactivity. In other instances, these complexes can be chiral, and capable of catalysing stereoselective reactions. In this review, we aim to highlight the catalytic applications of cycloruthenated complexes in organic synthesis, emphasising the recent advancements in this field.

Highlights

  • The discovery and development of novel and efficient catalysts that can facilitate new chemical transformations has been a longstanding challenge in chemical synthesis

  • Since this review aims to showcase the use of cycloruthenated complexes as catalysts in various transformations, we have focused our attention on cyclometallated adamantyl-N-heterocyclic carbene (NHC) ruthenium complexes in Z-selective metathesis reactions

  • The asymmetric ring-closing metathesis of trienes, along with an example of asymmetric cross metathesis to forge allylic stereocentres was developed (Scheme 29).[58]. In another example that illustrates the effectiveness of the nitrato-based ruthenium catalysts, Grubbs described the highly Z-selective cross metathesis reaction of different terminal ole ns, synthesising for the rst time, Z-a,b-unsaturated acetals

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Summary

Introduction

The discovery and development of novel and efficient catalysts that can facilitate new chemical transformations has been a longstanding challenge in chemical synthesis. Compared to other transition metals (e.g. palladium, platinum, and rhodium), ruthenium is inexpensive, making its use in both academic and industrial settings more economically viable.[5] Ruthenium complexes are o en straightforward to synthesise and Michael Findlay obtained his undergraduate degree in Chemistry from the University of Oxford in 2017, completing his nal year research project in the group of Professor Michael Willis. He is currently studying towards his PhD at the University of Manchester, under the supervision of Professor Igor Larrosa. We hope that by highlighting the recent advances and existing challenges in this eld, this review can encourage further research into the development of useful new catalysts for organic synthesis

C–H functionalisation
Alkylation
Chiral-at-ruthenium catalysis
Z-selective olefin metathesis
Transfer hydrogenation
Enantioselective cyclopropanation
Oxidative cyclisation and cycloaddition
Conclusions and outlook
Findings
Conflicts of interest
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