Allylic rearrangement

Pathology

Organic chemistry

Reactive intermediate

Reactivity (psychology)

Cyclohexene

Catalysis

Medicinal chemistry

Chemistry

Cyclam

Alternative medicine

Metal

Hydrogen peroxide

Regioselectivity

Medicine

Photochemistry

Angewandte Chemie International Edition

The generation of a nonheme oxoiron(IV) intermediate, [(cyclam)Fe IV (O)(CH 3 CN)] 2+ ( 2 ; cyclam=1,4,8,11‐tetraazacyclotetradecane), is reported in the reactions of [(cyclam)Fe II ] 2+ with aqueous hydrogen peroxide (H 2 O 2 ) or a soluble iodosylbenzene ( s PhIO) as a rare example of an oxoiron(IV) species that shows a preference for epoxidation over allylic oxidation in the oxidation of cyclohexene. Complex 2 is kinetically and catalytically competent to perform the epoxidation of olefins with high stereo‐ and regioselectivity. More importantly, 2 is likely to be the reactive intermediate involved in the catalytic epoxidation of olefins by [(cyclam)Fe II ] 2+ and H 2 O 2 . In spite of the predominance of the oxoiron(IV) cores in biology, the present study is a rare example of high‐yield isolation and spectroscopic characterization of a catalytically relevant oxoiron(IV) intermediate in chemical oxidation reactions.

Trapping of a Highly Reactive Oxoiron(IV) Complex in the Catalytic Epoxidation of Olefins by Hydrogen Peroxide