Dirhodium(II) paddlewheel complexes are highly modular and have been extensively used as catalysts in diazo-mediated reactions such as cyclopropanation and C-H functionalization. The axial sites of the complex can be also be modulated as a control element, but this type of customization has traditionally led to subpar performance in diazo-mediated reactions. Recently, our group reported the synthesis of dirhodium (II) paddlewheels with tethered, axially coordinated ligands that have been able to overcome this inherent issue in cyclopropanation and Si-H insertions. Herein, we report a microwave-assisted method of synthesizing these catalysts and their application to the cyclopropanation of alkenes with ethyl diazoacetate, a non-selective diazo substrate. Catalysis of this transformation was determined to be enhanced by using the catalysts with tethered thioether ligands. X-ray crystallography, cyclic voltammetry, UV/Vis, and computational studies were conducted to help rationalize the enhanced performance.

Influence of tethered thioether ligands on Rh(II)-catalyzed cyclopropanation with ethyl diazoacetate

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.