Two strategies towards amide functionalization will be presented: a photoredox/Ni system able to facilitate amide arylation and an unexpected protocol where amide alkylation is promoted by K3PO4, with no metal added. From a mechanistic perspective, the Ni catalyzed arylation procedure is inspired by previous reports that describe the use of photoredox catalysts to accelerate reductive elimination upon oxidation of Ni(II) to Ni(III) complexes. While previous reports primarily focused on the arylation of nucleophilic groups and require the use of strong organic bases able to deprotonate the nucleophile and facilitate single electron transfer steps, amide arylation is accomplished in the presence of weak inorganic bases. Despite the challenges arising from the low basicity and nucleophilicity of this functional group, the arylated amides are obtained in good yields. Additionally, the use of K3PO4 to facilitate amide alkylation of a wide variety of amides will be discussed. This complementary approach to amide functionalization enables access to secondary and tertiary amides and tolerates steric bulk, electron withdrawing, and donating groups in both coupling partners as well as the presence of functional group like aryl bromides, incompatible with the metal-based strategies. Preliminary results on the mechanism of this procedure will be introduced.

New approaches to amide arylation and alkylation under mild conditions

ACS Spring 2022

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