Oxidant-Free α-Amination of Ketones with Nitrogen Nucleophiles

α-Amino carbonyl compounds are valuable building blocks for diverse pharmaceuticals and natural products. However, current synthetic methods often rely on specialized nitrogen reagents, stoichiometric oxidants, or metal catalysts, highlighting the need for powerful and green synthetic methodologies. Herein, we report an unprecedented method for the synthesis of α-amino ketones from α-chloroketones using available nucleophilic amines. The process features a ring-opening rearrangement of cyclopropanones to generate para -quinone methide intermediates, enabling subsequent 1,6-additions with N -nucleophiles. This reaction demonstrates exceptional chemo- and regioselectivity and is compatible with a diverse array of substrates, including aliphatic and aromatic amines. Notably, this transformation requires neither external oxidants nor metal catalysts.