Aryl enol acetates and DMF could promote radical difluoroalkylation of aryl enol acetates to generate α,α‐difluoro‐γ‐ketoacetates without a catalyst, an oxidant, or a base. When using different bases, β‐fluoroenones and β‐enaminones were synthesized by controllable C−F bond activation. These transformations provide an alternative method for the cascade difluoroalkylation and C−F bonds activation of aryl enol acetates.

A novel tandem N‐dealkylation and N‐methyl aerobic oxidation of tertiary aromatic amines to N‐arylformamides using copper and TEMPO has been developed. This methodology suggested an alternative synthetic route from N‐methylarylamines to N‐arylformamides.

A copper‐phosphine system (Cu(OAc)2 and t‐Bu3P⋅HBF4) was used to synthesize α‐aminophosphonates and phosphoramides from various aromatic amines and trialkyl phosphites under oxygen atmosphere. With this Cu−P system, α‐aminophosphonates containing C−P bonds were generated from N,N‐dimethylanilines or N‐methylanilines and trialkyl phosphites; phosphoramidates containing N−P bonds were produced from N‐benzylanilines and trialkyl phosphites. This strategy provided a convenient and efficient method for the synthesis of phosphorous compounds. The compounds containing phosphoryl group attracted extensive attention due to their biological activities and wide applications.[1,2] The α‐aminophosphonates have been applied in medicine and agriculture such as anticancer drugs, antibiotics, antibacterial agents, and enzyme inhibitors.[1] And phosphoramides could be served as antibiotics, prodrugs, flame retardants, and ligands.[2]