Recent Advances in the Synthesis and Applications of α-Ketothioesters

α-Ketothioesters have only recently received widespread attention as synthetic intermediates and an impressive growth has been realized for their utilization in synthetic and medicinal chemistry. Several elegant approaches such as oxidative thioesterification and radical coupling allow for their convenient synthesis from easily available starting materials, e. g., methyl ketones, alkenes, alkynes, and α-hydroxyketones. Due to their multifaceted and diverse reactivities, several important reactions such as C(O)−S bond cleavage and S-migration with various C-, N-, and O-based nucleophiles, Ni-catalyzed mono- and double-decarbonylations, enantioselective carbonyl-ene reaction, diastereoselective hetero Diels-Alder reactions with olefins, and different types of cyclization reactions have been observed. They have also proven to be a valuable tool for the synthesis of heterocycles, pharmaceutically relevant anticancer drug, and natural product. However, in comparison to other 1,2-dicarbonyl derivatives such as α-ketooxoesters, α-ketoamides, and α-ketoaldehydes, they are much less appreciated as synthetic intermediates. This review summarizes the recent advancements achieved in the synthesis of α-ketothioesters as well as their applications in the development of new reactions for the formation of C−C, C−N, and C−O bonds, including multiple bond-forming processes. (Figure presented.).