First palladium- and nickel-catalyzed oxidative diamination of alkenes: Cyclic urea, sulfamide, and guanidine building blocks

Muñiz, Kilian; Hövelmann, Claas H.; Streuff, Jan; Campos-Gómez, Esther

doi:10.1351/pac200880051089

Pure Appl. Chem., 2008, Vol. 80, No. 5, pp. 1089-1096

http://dx.doi.org/10.1351/pac200880051089

First palladium- and nickel-catalyzed oxidative diamination of alkenes: Cyclic urea, sulfamide, and guanidine building blocks

Kilian Muñiz, Claas H. Hövelmann, Jan Streuff and Esther Campos-Gómez

Laboratory for Homogeneous Catalysis and Molecular Synthesis, Institute of Chemistry, UMR 7177, Université Louis Pasteur, 4 rue Blaise Pascal, F-67000 Strasbourg Cedex, France

Abstract: We recently reported the first catalytic diamination of alkenes. This protocol calls for the use of Pd(II) as catalyst in combination with PhI(OAc)₂ as terminal oxidant and furnishes the final diamines as cyclic ureas. It consists of an unprecedented two-step reaction of aminopalladation and C_sp3-N-bond formation involving a Pd(IV) species. Introduction of Ni(II) catalysts for homogeneous oxidation allows for an efficient diamination with sulfamides, which lead to convenient liberation of the free diamines. In related protocols, the substrate scope of the diamination has been broadened to the formation of cyclic guanidines.