Hydroxylamine Hydrochloride as Bifunctional Reagent for Aminochlorination of Alkenes via Iron Catalysis

While O-protected hydroxylamine derivatives have enabled various alkene amination reactions, their practical utility remains limited by poor atom economy and the requirement for multistep synthesis. Herein, we demonstrate that bulk chemical hydroxylamine hydrochloride serves as a bifunctional reagent for aminochlorination of alkenes via iron catalysis, producing water as the sole byproduct. An acidic medium is essential for the success of this transformation, operating by promoting the addition of the putative aminyl radical to alkene. This method exhibits a broad substrate scope and excellent functional group tolerance and is effective for the late-stage functionalization of complex molecules. Notably, this reaction features a delayed chlorine transfer compared to the existing method. This mechanistic divergence grants exceptional selectivity in the transformation of substrates like 1,6-dienes and camphene.