Aliphatic amines are important and ubiquitous moieties in bioactive molecules. Oxidative alkene functionalization is an ideal approach to forming value-added amine products as it leverages simple, abundant feedstock starting materials to rapidly build and diversify molecular complexity. However, the coupling of alkenes and amines traditionally proceeds via nitrogen activation requiring use of electrophilic nitrogen reagents or electronically deactivated nitrogen pronucleophiles that install a limited range of electron-withdrawing N-substituents on the final alkylamine product. We describe herein a novel, electrochemical approach to C-N bond formation that couples abundant unactivated alkenes and abundant aliphatic amines for the synthesis of N-alkyl aziridines and (Z)-allylic alkylamines, two versatile aliphatic amine synthons. Our dication pool strategy uses anodic oxidation of cheap, safe thianthrene in the presence of alkenes to generate versatile dielectrophiles that undergo subsequent substitution in a one-pot, two-operation process. Key to this strategy is the decoupling of substrate activation and substitution, enabling a wide range of oxidatively sensitive amines as amenable nucleophiles and greatly expanding the scope of aliphatic amine products.

Coupling alkenes and amines via a dication pool strategy

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