Cleavage of C(aryl)−CH ₃ Bonds in the Absence of Directing Groups under Transition Metal Free Conditions

Organic chemists now can construct carbon–carbon σ-bonds selectively and sequentially, whereas methods for the selective cleavage of carbon–carbon σ-bonds, especially for unreactive hydrocarbons, remain limited. Activation by ring strain, directing groups, or in the presence of a carbonyl or a cyano group is usually required. In this work, by using a sequential strategy site-selective cleavage and borylation of C(aryl)−CH ₃ bonds has been developed under directing group free and transition metal free conditions. Methyl groups of various arenes are selectively cleaved and replaced by boryl groups. Mechanistic analysis suggests that it proceeds by a sequential intermolecular oxidation and coupling of a transient aryl radical, generated by radical decarboxylation, involving a pyridine-stabilized persistent boryl radical.