Reactivity and kinetic-mechanistic studies of regioselective reactions of rhodium porphyrins with unactivated olefins in water that form beta-hydroxyalkyl complexes and conversion to ketones and epoxides

摘要

This article reports on the selective oxidation of unactivated alkenes to ketones and epoxides through the intermediacy of beta-hydroxyalkyl rhodium porphyrin complexes which are formed by reactions of terminal alkenes with tetra(p-sulfonatophenyl)porphyrin rhodium(III) complex. The beta-hydroxyalkyl rhodium porphyrin complexes in water undergo beta-C-H elimination to produce ketones in aqueous pH 9.0 solutions and O-H deprotonation in KOH/DMSO solutions resulting in the rapid and quantitative intramolecular nucleophilic displacement to form 1,2-epoxyalkanes.