Hydrodefluorination of polyfluoro-2-naphthylamines by Zn in aqueous NH3: A correlation of the product distribution and the computationally predicted regioselectivity of the substrate radical anion fragmentation

The combined results of chemical, CVA and quantum-chemical studies provide a mechanistic insight into an interrelation between the regioselectivities of polyfluoro-2-naphthylamines hydrodefluorination and fragmentation of the substrate radical anions. [Display omitted] ► Polyfluoro-2-naphthylamines are reductively hydrodefluorinated by Zn in aq. NH3. ► The reduction energetics has been characterized by CVA measurements. ► The structures of substrate radical anions have been quantum-chemically calculated. ► The radical anions fragmentation regioselectivity correlates with their structures. ► The product distribution is controlled by the radical anions fragmentation. Hydrodefluorination of heptafluoro-2-naphthylamine and its less fluorinated analogues by zinc in aqueous ammonia has been explored with respect to the possibility to occur and to rationalize the product distribution in terms of the mechanism including formation and fragmentation of a polyfluoroarene radical anion.