Diastereoselective Olefin Amidoacylation via Photoredox PCET/Nickel-Dual Catalysis: Reaction Scope and Mechanistic Insights

The selective 1,2-aminoacylation of olefins provides opportunities for the rapid construction of nitrogen-containing molecules. However, the lack of CO-free acylation reactions has limited their application. By using photoredox proton-coupled electron transfer (PCET)/Ni dual-catalysis, a highly regio- and diastereoselective amidoacylation of unactivated olefins has been developed. Various acyl electrophiles are compatible, including alkyl- and aryl acyl chlorides and anhydrides, as well as in situ activated carboxylic acids. Hammett studies and other mechanistic experiments to elucidate features of the diastereoselectivity, a transient absorption study of the PCET step, as well as computational evidence, provide an in-depth understanding of the disclosed transformation.