Oxygen-Dependent Ligand-Controlled Iron-Catalyzed Chemoselective Synthesis of Olefins and Vinyl Nitriles.

An oxygen-dependent ligand-controlled chemoselective synthesis of vinyl nitriles and E -olefins by coupling a variety of alcohols and benzyl cyanides, catalyzed by a well-characterized, air-stable, easy-to-prepare Fe(II) catalyst ( 1a ) bearing a redox-active arylazo pincer ( L 1a ) is reported. The azo-moiety of the ligand backbone acts as an electron and hydrogen reservoir, enabling catalyst 1a to efficiently produce a broad spectrum of vinyl nitriles and E -olefins in moderate to good yields selectively under an oxygen and argon atmosphere, respectively.