An effective and selective non-heme iron-catalyzed hydroxylation of alkane C–H bonds

Abstract

Selective hydroxylation of non-activated alkyl C–H bonds remains a contemporary challenge in organic synthesis, while these transformations in nature are mainly mediated by iron-dependent enzymes under mild conditions. Herein, mononuclear nonheme iron complexes 1 and 2 demonstrate excellent selectivity in the oxidation of alkanes, including adamantane, cis-1,2-dimethylcyclohexane and cycloalkanes under ambient conditions. A high alcohol/ketone (A/K) ratio of 27.9 and a total turnover number of 128 were obtained in cyclohexane oxidation. Even in the presence of high water concentrations, the catalyst is more reactive towards alkane oxidation than water oxidation. A combination of high-resolution mass spectrometry (HR-MS) and EPR analysis revealed the formation of an Fe^III-peroxo species.