Reactivity of Anomalous Aziridines for Versatile Access to High Fsp

ConspectusThe manipulation of strained rings is a powerful strategy for accessing the valuable chemical frameworks present in natural products and active pharmaceutical ingredients. Aziridines, the smallest N-containing heterocycles, have long served as building blocks for constructing more complex amine-containing scaffolds. Traditionally, the reactivity of typical aziridines has been focused on ring-opening by nucleophiles or the formation of 1,3-dipoles. However, over the past decade, our group has pioneered highly chemo-, site-, and stereoselective Ag- and Rh-catalyzed nitrene transfer (NT) reactions of allenes and alkenes to furnish unusual, or "anomalous", aziridines. The unique features of these aziridines, coupled with our ability to control the fate of strained intermediates resulting from diverse reactions of these precursors, allow for their transformation to densely substituted, stereochemically complex N-heterocyclic structures that would otherwise be difficult to access using conventional strategies. Our research is driven by a keen interest in versatile synthetic approaches that explore high Fsp