Oxidative Interception of the Hydroamination Pathway: A Gold-Catalyzed Diamination of Alkenes

A complimentary diamination of alkenes by using homogeneous gold catalysts is described. The reaction is one of very few examples of homogeneous gold oxidation catalysis and proceeds with high selectivity under mild conditions. Individual steps of the suggested catalytic cycle were investigated on isolated model gold complexes, and new pathways for gold-catalyzed amination reactions were established. The key step is an intramolecular alkyl-nitrogen bond formation from a gold(III) intermediate. This process validates the concept of reductive elimination from high oxidation catalyst states for this type of C-N bond forming reactions.