Arene Amination Instead of Fluorination: Substitution Pattern Governs the Reactivity of Dialkoxybenzenes with Selectfluor

Arene
substitution patterns are well-known to affect the regioselectivity
of a given transformation but not necessarily the type of reactivity.
Herein, we report that the substitution pattern of alkoxyarenes dictates
whether a putative one-electron or two-electron reaction predominates
in reactions with Selectfluor. A series of amination products is presented,
resulting from the single-electron oxidation of electron-rich arenes
followed by direct C–H to C–N bond formation. We demonstrate
the ability of this transformation to synthesize medicinally and biologically
relevant nitrogen heterocycles. Lastly, this unusual “mechanistic
switch” is probed with computational chemistry and competition
experiments.