Cobalt-Catalyzed Decarboxylative Allylations: Development and Mechanistic Studies

In recent years, there has been a concerted drive to develop methods that are greener and more sustainable. Being an earth-abundant transition metal, cobalt offers an attractive substitute for commonly employed precious metal catalysts, though reactions engaging cobalt are still less developed. Herein, we report a method to achieve the decarboxylative allylation of nitrophenyl alkanes, nitroalkanes, and ketones employing cobalt. The reaction allows for the formation of various substituted allylated products in moderate-excellent yields with a broad scope. Additionally, the synthetic potential of the methodology is demonstrated by the transformation of products into versatile heterocyclic motifs. Mechanistic studies revealed an in situ activation of the Co(II)/dppBz precatalyst by the carboxylate salt to generate a Co(I)-species, which is presumed to be the active catalyst. Sustainable catalysis: The development of a cobalt-catalyzed decarboxylative allylation of nitrophenyl alkanes, nitroalkanes, and ketones is accomplished. The protocol offers the regioselective synthesis of various allylated products with broad functional group tolerance. Mechanistic studies revealed an unusual activation of Co(II)-salts using new organoreductants.image