Visible-Light-Initiated, Nickel-Catalyzed Aminocarbonylation of Alkynyl Iodides to 2-Ynamides

Context and methodology

The development of new, broadly applicable methods for amide bond formation remains a central objective in synthesis, particularly given the prevalence of amides in medicinally relevant compounds. Despite the value of 2-ynamides as versatile structural motifs, existing aminocarbonylative approaches rely exclusively on Pd catalysis and require relatively harsh conditions. Herein, we disclose a visible-light-initiated, Ni-catalyzed aminocarbonylation of alkynyl iodides that proceeds under low carbon monoxide pressure, providing an earth-abundant catalytic platform for accessing 2-ynamides. Mechanistic investigations support the light-triggered generation of catalytically active Ni(I) species that initiate a thermally sustained carbonylative Ni(I)/Ni(III) manifold. The method features operational simplicity and a broad substrate scope, accommodating a wide range of alkynyl iodides and amines to afford the corresponding 2-ynamides in good to excellent yields.

Technical details

A compound list is provided, matching each compound name and number with the corresponding experiment number. The uploaded ZIP files contain the NMR spectra for all substrates and products, as well as ATR-IR and HRMS data for all new compounds. Specialized software, such as MestreNova and MassHunter, is required to open and process the NMR and HRMS data. ATR-IR data are provided as CSV files.

The publication and its Supporting Information can be found as open-access files on the publisher's website.