Metal–Ligand Cooperation for Iron(II)‐Catalyzed Direct Wittig‐Type Olefination from Alcohols in Air

An iron‐catalyzed one‐pot tandem in situ oxidation–Wittig reaction is reported for the synthesis of alkenes. Using a bench‐stable Fe(II) catalyst with a redox‐noninnocent 2‐((4‐chlorophenyl)diazenyl)‐1,10‐phenanthroline ligand scaffold, a broad spectrum of substituted E olefins is synthesized in good yields by the reaction of alcohols with phosphorus ylides. Control reactions and spectroscopic studies indicate synergistic participation of the ligand, which acts as a reservoir of electrons and hydrogen, during the dehydrogenative coupling of alcohols with the phosphorus ylides.