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Taming Keteniminium Reactivity by Steering Reaction Pathways: Computational Predictions and Experimental Validations
Mark A Maskeri1, Anthony J Fernandes2, Giovanni Di Mauro2
1Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.
Abstract:
Keteniminium ions, the nitrogen analogues of ketenes, exhibit high reactivity toward olefins and π-systems. Previous results from the Maulide group demonstrated an unexpected propensity for an alternative intramolecular Belluš-Claisen-type rearrangement rather than an expected intramolecular (2 + 2) cycloaddition. We have conducted a cooperative density functional theory/experimental investigation of this process, seeking insights into the competition between the observed Claisen-type reaction and the historically expected (2 + 2) cyclization. Our calculations revealed a surprisingly small difference in the free energy barrier between these two intramolecular reactions. Further theoretical and experimental investigations probe the electronics of the substrate, rationalize a competing deallylation side reaction, and demonstrate the proof-of-concept for an enantioselective (2 + 2) variant.
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