From Radical Polarity Inversion to Amine Synthesis: Alkene Functionalization with α-Ammoniomethyl Radicals

Tertiary alkylamines are important structural motifs in pharmaceuticals, and aminomethyl functionalization of alkenes offers a direct approach to their synthesis. However, conventional methods employing nucleophilic α-aminomethyl radicals have largely been limited to activated, electron-deficient alkenes. Here, we describe an amine umpolung strategy in which quaternization reverses radical polarity, enabling reactions with unactivated, alkyl-substituted alkenes and providing access to a diverse range of tertiary alkylamines. This work introduces cation-state control as a strategy for unlocking new reactivity in amine-based molecules for organic synthesis.