Amination and hydrodefluorination of aryl fluorides promoted by solvated electrons.

Cross‐coupling reactions for constructing C‐N bonds represent a pivotal advancement in chemical science. Traditional methodologies, including nucleophilic aromatic substitution (SNAr) and transition metal‐catalyzed cross‐couplings, have limitations concerning aryl scope, reliance on toxic and costly transition‐metal catalysts, and issues related to atom economy and waste generation from ligands and additives. In this work, we introduce a novel method for aminating neutral, electron‐rich, and electron‐deficient aryl halides, eliminating the need for transition metals. Our approach involves the activation of aryl halides using solvated electrons generated from granulated lithium and sonication. This serves as a sustainable source of reducing power, facilitating the efficient formation of C‐N bonds under near ambient conditions. Competitive selectivity studies between halide and ester functionalities were explored. Reaction scope and conducted mechanistic studies support the proposed radical‐nucleophilic substitution (SRN1) mechanism for the reaction. Notably, the developed reaction has a highly competitive reductive dehalogenation pathway during the C‐N coupling reaction, and this mechanistic divergency was thoroughly explored. This work not only broadens the scope of C‐N coupling reactions which typically employs aryl bromides and iodides and rarely aryl fluorides which is also equally abundant, but also introduces a new way to do C‐N coupling reactions using solvated electrons.