Mechanistic insights into the allylic oxidation of aliphatic compounds by tetraamido iron(V) species: A C–H vs. O–H bond activation

摘要: The main challenges in synthetic organic chemistry are chemoselective oxidation of C–H bonds by natural complexes under mild conditions. Heme and non-heme metal with several oxidants such as dioxygen, hydrogen peroxide, m-chloroperbenzoic acid etc. used for the catalytic aliphatic bonds. Metal catalyzed allylic compounds results attractive intermediates these very useful pharmaceutical industries. Here we have reported electronic structures also first time mechanistic detail selective cyclohex-2-enol an oxidant iron oxo species using hybrid density functional theory incorporating dispersion effects. Our DFT show that a significant spin on ferryl oxygen plays important role activating O–H cyclohex-2-enol. reaction can be feasible via (pathway a) b) bond activation. initial abstraction is rate-determining step both pathways. A carbon atoms shows O–H/C–H activation occurs through homolytic cleavage. investigation studied mechanism two-state reactivity whereas proceed single state reactivity. By mapping energy profiles, found relatively favored over attack. Furthermore, exchange electrons structural parameters during transition states control help to design catalysts better efficiency/selectivity reactions.