Though ubiquitous in nature, small molecules with carbon-nitrogen bonds are often difficult to prepare in the laboratory. Arguably, the most efficient method of C-N bond access is through nitrene intermediates. Nitrenes, neutral, monovalent, high-energy species, are can be effective as intermediates for skeletal rearrangements and electrophilic insertion into a variety of bonds, such as alkenes. Reactions reliant on the use of nitrenes often lack regiocontrol and selectivity. In this work, we investigate the formation of nitrenes by oxidation of carbamates using a hypervalent iodine oxidant and subsequent transfer to an alkene by means of a dirhodium catalyst, resulting in aziridination, C-N insertion, or [3 + 2] cyclization. Through optimization protocols, we evaluate the identity of the hypervalent iodine oxidant and the dirhodium catalyst in controlling nitrene formation and reactivity. We also report the effects of alkene geometry and substitution in the resulting products.

Generation of carbamate-derived nitrenes and evaluation of their inter- and intramolecular reactivity with alkenes

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.