Photoredox Driven Amide Synthesis from Tertiary Amines and Carboxylic Acids via C-N Bond Cleavage

This manuscript describes a visible-light-promoted, Ir-catalyzed, aerobic protocol for amide synthesis from tertiary amines and carboxylic acids. The reaction likely proceeds through α-C-H oxidation of the tertiary amine, followed by C-N bond cleavage via hydrolysis to the secondary amine intermediate. Concurrently, the additive CF₃SO₂Na reacts to activate the carboxylic acid via an acyl fluoride intermediate, which in turn reacts with the secondary amine to yield the product amides. The established conditions tolerate a wide variety of carboxylic acid substrates, including complex carboxylic acids. Furthermore, previously unreactive amine substrates such as N-methyl morpholine and tri-n-butyl amine are shown to react readily.