Oxoiron(v) mediated selective electrochemical oxygenation of unactivated C–H and CC bonds using water as the oxygen source

Abstract

An efficient electrochemical method for the selective oxidation of C–H bonds of unactivated alkanes (BDE ≤97 kcal mol⁻¹) and CC bonds of alkenes using a biomimetic iron complex, [(bTAML)Fe^III-OH₂]⁻, as the redox mediator in an undivided electrochemical cell with inexpensive carbon and nickel electrodes is reported. The O-atom of water remains the source of O-incorporation in the product formed after oxidation. The products formed upon oxidation of C–H bonds display very high regioselectivity (75 : 1, 3° : 2° for adamantane) and stereo-retention (RC ∼99% for cyclohexane derivatives). The substrate scope includes natural products such as cedryl acetate and ambroxide. For alkenes, epoxides were obtained as the sole product. Mechanistic studies show the involvement of a high-valent oxoiron(V) species, [(bTAML)Fe^V(O)]⁻ formed via PCET (overall 2H⁺/2e⁻) from [(bTAML)Fe^III-OH₂]⁻ in CPE at 0.80 V (vs. Ag/AgNO₃). Moreover, electrokinetic studies for the oxidation of C–H bonds indicate a second-order reaction with the C–H abstraction by oxoiron(V) being the rate-determining step.