Recent Advances in the Catalytic Synthesis of α-Ketoamides

alpha-Ketoamides and their derivatives are key constituents of natural products, biologically relevant molecules, drug and drug candidates, and functional materials. Further, they are versatile and valuable intermediates and synthons in a number of functional group transformations and total syntheses. In recent years tremendous growth has been realized in the development of synthetic methods for a-ketoamide preparation and their applications in synthetic and medicinal chemistry. Among the various catalytic methods of alpha-ketoamide formation, two approaches, namely double aminocarbonylation and oxidative amidation, have received much more attention and have been greatly studied because of the ready availability of the starting materials, use of carbon monoxide (CO) as a direct source of carbonyl functionalities, and use of molecular oxygen (O-2) or air as a green terminal oxidant and/or reactants. Catalyzed alpha-ketoamide formation can be roughly classified into metal- and nonmetal-catalyzed processes. In the context of metal catalysis, most reactions involving metals are performed using palladium (Pd) and copper (Cu); however, other metals such as gold (Au), silver (Ag), and iron (Fe) based catalysts have also been investigated to some extent. On the other hand, nonmetal-catalyzed alpha-ketoamide syntheses are mainly restricted to iodine-based catalysts in the presence or absence of other promoters. Our objective in this review is to highlight the important research endeavors related to catalytic alpha-ketoamide synthesis, which include the trends in the catalytic synthesis of alpha-ketoamides, new breakthroughs, and recent advances up to March 2016.