Biasing Divergent Polycyclic Aromatic Hydrocarbon Oxidation Pathway by Solvent-Free Mechanochemistry.

Precise control in reaction selectivity is the goal in modern organic synthesis, and it has been widely studied throughout the synthetic community. In comparison, control of divergent reactivity of a given reagent under different reaction conditions is relatively less explored aspect of chemical selectivity. We herein report an unusual reaction between polycyclic aromatic hydrocarbons and periodic acid HIO (), where the product outcome is dictated by the choice of reaction conditions. That is, reactions under solution-based condition give preferentially C-H iodination products, while reactions under solvent-free mechanochemical condition provide C-H oxidation quinone products. Control experiments further indicated that the iodination product is not a reaction intermediate toward the oxidation product and vice versa. Mechanistic studies unveiled an in situ crystalline-to-crystalline phase change in during ball-milling treatment, where we assigned it as a polymeric hydrogen-bond network of . We believe that this polymeric crystalline phase shields the more embedded electrophilic ═O group of from C-H iodination and bias a divergent C-H oxidation pathway (with I═) in the solid state. Collectively, this work demonstrates that mechanochemistry can be employed to completely switch a reaction pathway and unmask hidden reactivity of chemical reagents.