Copper-catalyzed transformation of a C-H bond into a C-N bond is a promising protocol for the synthesis of value-added nitrogen-containing compounds. Previous work from our laboratory showed a discrete �-diketiminato dicopper nitrene {[Cl2NN]Cu}2(�-NAd) as key intermediate in the catalytic amination of secondary benzylic and unactivated secondary aliphatic C-H bonds with organoazides. We proposed that the dicopper nitrene species  dissociates into a terminal copper nitrene, the reactive species for C-H bond functionalization. This presentation focuses on the mechanistic aspects of this reaction using alkylazides (N3tBu, N3Cy, N3CH2CH2Ph), as nitrene sources. Kinetics of the C-H amination of ethylbenzene was explored using a discrete {[Cl2NN]Cu}2(�-NtBu) species to identify the dependence of the rate on substrate and monocopper {{[Cl2NN]Cu} concentrations. In addition, we employ the use of stereochemical probes as C-H substrates like 1,4-dimethylcyclohexane and cyclopropyl radical clock to provide insight into the nature of nitrene insertion.

Understanding the mechanism of C-H amination via Cu(I) ß-diketiminato alkylnitrenes

243rd National Meeting (2012)

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