Discrete Late Metal Nitrenes in Catalytic C-H Amination

Catalytic C-H amination offers the opportunity to directly convert C-H bonds into amine functionalities without the need for prior chemical modification of these normally unreactive C-H bonds. Electrophilic, late transition metal-nitrene complexes [M]=NR are believed to be the active intermediates in this challenging transformation, providing greater chemoselectivity than free nitrenes themselves. Using well-defined -diketiminato complexes of Co, Ni, and Cu, we demonstrate the synthesis of discrete metal-nitrene complexes which enables a detailed examination of their electronic structure as well as reactivity towards a variety of substrates. These fundamental inorganic synthetic studies allow for the rational development of a catalytic system for the efficient amination of a wide variety of sp3-hybridized C-H bonds with organoazides.

Leading References:

(1) "Transient Terminal Cu-Nitrene Intermediates from Discrete Dicopper Nitrenes" Badiei, Y. M.; Krishnaswamy, A.; Melzer, M.; Warren, T. H. J. Am. Chem. Soc. 2006, 128, 15056-15057.

(2) "A Terminal Ni(III)-Imide with Diverse Reactvity Pathways" Kogut, E.; Wiencko, H. L.; Zhang, L.; Cordeau, D. C.; Warren, T. H.* J. Am. Chem. Soc. 2005, 127, 11248-11249.

(3) "[Me2NN]Co(6-toluene): O=O, O=N, and N=N Bond Cleavage Provides -Diketiminato -Oxo and Imido Complexes" Dai, X.; Kapoor, P.; Warren, T. H. J. Am. Chem. Soc. 2004, 126, 4798-4799.

For more information contact Dr. Jean-Luc Bredas (404-385-4986).