Metal catalyzed synthetic reactions via aerobic oxidation as a key step

New aerobic oxidative metal catalyzed synthetic reactions are described: The Cu(II) complex catalyzed the acylation of thioester in Wittig lactonization under neutral conditions and the dissymmetrization of symmetric dithiomalonates via selective monoacylation. The key step in this reaction was the formation of an acylketene, the stability of which would contribute to selectivity. The aerobic Rh/C-catalyzed oxidative homo- and cross-coupling of aryl amines was developed. The coupling reactions afforded symmetrical and nonsymmetrical biaryl amines in excellent yields. These reactions provide a mild, operationally simple, and efficient approach for the synthesis of biaryls which are important to pharmaceutical and materials chemistry.