Date of Submission

Spring 2020

Academic Program

Chemistry

Project Advisor 1

Prof. Emily McLaughlin

Abstract/Artist's Statement

Nitrogen insertion reactions are an atom economical methodology that presents significant potential in carbon nitrogen bond construction. Specifically, the use of nitrenes as neutral, reactive species as substrates for nitrogen insertion is relatively understudied compared to their carbon analog, carbene. Even further, carbamates as “un-oxidized” nitrenes, and concomitant dirhodium (II) catalysts, have been largely understudied for their efficacy in aziridination and/or C-H amination. In this study we examine the efficacy of a carbamate with a tethered olefin, a requisite moiety for intramolecular C-N bond formation, paired with varied dirhodium (II) catalysts to examine the catalysts’ influence on aziridination or C-H amination reaction pathways. In this work, we synthesize multiple dirhodium (II) compounds and carry out multiple microwave-mediated aziridination trials. During this process, it was gleaned that dirhodium (II) compounds, with carboxamidate ligands were inherently more stable due to increased pi- backbonding and often lower oxidation potentials, positively influencing the stability and reactivity of a rhodium-nitrene intermediate. The facile syntheses of dirhodium (II) compounds, and microwave-assisted nitrogen insertion shows promise for further development of a reliable aziridination protocol.

Open Access Agreement

On-Campus only

Creative Commons License

Creative Commons License
This work is licensed under a Creative Commons Attribution-Noncommercial-No Derivative Works 4.0 License.

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