Theoretical Study of the Reactivity of Phenyl Radicals Toward Enol Acetates

Arylation reactions are an important class of reactions and allow the synthesis of natural and synthetic products. Despite the efficient, but high cost and toxic methodologies involving transition metals, radical arylations have gained importance after the advent of photoredox catalysis. Arylation of enol acetates is an important tool for obtaining aryl ketones but the scope of the reaction is limited to the pattern of substitution at phenyl radical and α-carbon of the enol. Theoretical calculations ((U)BHandHLYP/6-311G**) show that the polar effect is the key factor in this reaction. A good correlation of calculated rate constants with field effect explained why phenyl radicals with electron-withdrawing groups react faster toward enol acetate. The presence of alkyl groups at α carbon at the enol showed some influence of enthalpic effect but strong influence of steric effect, evidenced by great correlations with Taft and Charton parameters. Finally, substitution at β carbon showed no significant effect at reaction rates.