A Study of Intramolecular C-N Bond Formation: Synthesis and Reactivity of Dirhodium (II) Compounds for Aziridination
Date of Submission
Project Advisor 1
Prof. Emily McLaughlin
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.
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Mohamed, Waseer Kedar, "A Study of Intramolecular C-N Bond Formation: Synthesis and Reactivity of Dirhodium (II) Compounds for Aziridination" (2020). Senior Projects Spring 2020. 29.
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