Water-promoted deconstructive amination of alkenes through single-carbon deletion: access to fully substituted pyrroles

Abstract

Developing efficient methods for the deconstructive nitrogenation of alkenes remains challenging because carbon–carbon double bonds are generally resistant to cleavage under mild conditions. Here we report a catalyst-free, water-promoted deconstructive amination of electron-deficient dienes that proceeds through an unprecedented single-carbon deletion pathway. The transformation operates smoothly in water without photoirradiation, oxidants, or radical precursors, providing diverse fully substituted pyrroles. Mechanistic studies indicate a sequence involving initial aziridination followed by water-assisted C–C and C–N bond cleavage of a transient aziridine intermediate. Water plays a key role in enabling single-carbon extrusion and guiding selective skeletal reorganization. This approach offers high atom- and step-economy and complements existing oxidative and radical-based strategies. The mild conditions, broad substrate scope, and straightforward access to bioactive pyrrole analogs highlight the practical utility of this method. Overall, this work provides a mechanistically distinct route to carbon–carbon double bond deconstructive nitrogenation and expands the toolkit for heterocycle synthesis.