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Issue 44, 2020
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Tuning Rh(ii)-catalysed cyclopropanation with tethered thioether ligands

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Abstract

Dirhodium(II) paddlewheel complexes have high utility in diazo-mediated cyclopropanation reactions and ethyl diazoacetate is one of the most commonly used diazo compounds in this reaction. In this study, we report our efforts to use tethered thioether ligands to tune the reactivity of RhII-carbene mediated cyclopropanation of olefins with ethyl diazoacetate. Microwave methods enabled the synthesis of a family of RhII complexes in which tethered thioether moieties were coordinated to axial sites of the complex. Different tether lengths and thioether substituents were screened to optimise cyclopropane yields and minimise side product formation. Furthermore, good yields were obtained when equimolar diazo and olefin were used. Structural and spectroscopic investigation revealed that tethered thioethers changed the electronic structure of the rhodium core, which was instrumental in the performance of the catalysts. Computational modelling of the catalysts provided further support that the tethered thioethers were responsible for increased yields.

Graphical abstract: Tuning Rh(ii)-catalysed cyclopropanation with tethered thioether ligands

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Supplementary files

Article information


Submitted
28 Aug 2020
Accepted
26 Oct 2020
First published
26 Oct 2020

Dalton Trans., 2020,49, 15779-15787
Article type
Paper

Tuning Rh(II)-catalysed cyclopropanation with tethered thioether ligands

D. Cressy, C. Zavala, A. Abshire, W. Sheffield and A. Darko, Dalton Trans., 2020, 49, 15779
DOI: 10.1039/D0DT03019H

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