Iron(II)‐Catalyzed Biomimetic Aerobic Oxidation of Alcohols

We report the first Fe(II)‐catalyzed biomimetic aerobic oxidation of alcohols. The principle of this oxidation, which involves several electron‐transfer steps, is reminiscent of biological oxidation in the respiratory chain. The electron transfer from the alcohol to molecular oxygen occurs with the aid of three coupled catalytic redox systems, leading to a low‐energy pathway. An iron transfer‐hydrogenation complex was utilized as a substrate‐selective dehydrogenation catalyst, along with an electron‐rich quinone and an oxygen‐activating Co(salen)‐type complex as electron‐transfer mediators. Various primary and secondary alcohols were oxidized in air to the corresponding aldehydes or ketones with this method in good to excellent yields.