Dioxygen Controlled Chemodivergent Cross‐Coupling of Primary and Secondary Alcohols Using Noninnocent Azo Aromatic Complexes of Cobalt(II) as Catalysts

Herein, employing pincer like cobalt (II) complexes containing redox noninnocent azo‐benzimidazole ligand a switchable and chemodivergent catalytic cross‐coupling of primary and secondary alcohols is reported. The reactions are environmentally benign and atom efficient. It liberates water and hydrogen gas as the only byproducts. While the reaction in inert condition gives alkylated ketones, in presence of air as well as lower temperature and base loading selectively results in unsaturated ketones. Both the catalytic protocols have very good functional group tolerance. Thus, a wide range of substrates have been found to be effective for the synthesis of alkylated ketones as well as unsaturated ketones via dehydrogenative cross‐coupling reaction of alcohols. Several control experiments and kinetic studies were performed to elucidate the reaction pathways.