Kharasch and metalloporphyrin catalysis in the functionalization of alkanes, alkenes, and alkylbenzenes by t-BuOOH. Free radical mechanisms, solvent effect, and relationship with the Gif reaction

A study of the oxidation of alkanes, alkenes and alkylbenzenes by t-BuOOH based on the Kharasch reaction and Mn(III)- and Fe(III)-porphyrin catalysis shows that t-BuO. and t-BuOO. radicals are involved in these oxidations which are associated with the Gif reaction. The oxidation proceeds through removal of hydrogen from t-BuOOH by t-BuO. in nonbasic solvents, but is inhibited in solvents forming hydrogen bonds with t-BuOOH.