Reductive molybdenum‐catalyzed direct amination of boronic acids with nitro compounds

The synthesis of aromatic amines is of utmost importance in a wide range of chemical contexts. We report a direct amination of boronic acids with nitro compounds to yield (hetero)aryl amines. The novel combination of a dioxomolybdenum(VI) catalyst and triphenylphosphine as inexpensive reductant has revealed to be decisive to achieve this new C-N coupling. Our methodology has proven to be scalable, air and moisture tolerant, highly chemoselective and engages both aliphatic and aromatic nitro compounds. More-over, this general and step-economical synthesis of aromatic secondary amines show cases orthogonality to other aromatic secondary amines show cases orthogonality to other aromatic amine syntheses as it tolerates aryl halides and carbonyl compounds.Junta de Castilla y León (BU022G18),Junta de Castilla y León and FEDER (BU076U16 and BU291P18) and Ministerio de Economía y Competitividad (MINECO) (CTQ2016-75023-C2-1-P