6/22/2021 – Congratulations to Dylan, Diana, and Minji on their work on aziridine synthesis through coupling unactivated alkenes and primary amines via metastable dicationic intermediates. Out in Nature now!

Aziridines, three-membered nitrogen-containing cyclic molecules, are important synthetic targets. Their significant ring strain and resultant proclivity towards ring opening reactions makes them versatile precursors to diverse amine products and, in some cases, the aziridine functional group itself imbues important biological (e.g. anti-tumor) activity. Transformation of ubiquitous alkenes into aziridines is an attractive synthetic strategy but is typically accomplished using electrophilic nitrogen sources rather than widely available amine nucleophiles. Here, we demonstrate that unactivated alkenes can be electrochemically transformed into a metastable, dicationic intermediate that undergoes aziridination with primary amines under basic conditions. This new approach expands the scope of readily accessible N-alkyl aziridine products relative to state-of-the-art methods. A key strategic advantage of this new approach is that oxidative alkene activation is decoupled from the aziridination step, allowing a wide range of commercially available but oxidatively sensitive amines to act as coupling partners for this strain-inducing transformation. More broadly, this work lays the foundations for a diverse array of difunctionalization reactions using this dication pool approach.