Although there have been significant advances in the field of metal-catalyzed oxidative amination, particularly in the context of C-H amination and aziridination reactions, this field has been dominated by the usage of late transition metals, which are often expensive and/or toxic. Conversely, titanium is a highly abundant, cheap, and nontoxic transition metal. However, titanium chemistry is dominated by the +4 oxidation state, thus catalytic redox processes are rare. Recently, our group has discovered several new Ti-catalyzed oxidative alkyne carboamination reactions. In expanding on amination coupling partners beyond alkynes, we have found that this same system can couple nitrenes with terminal methylenecyclopropanes using diazenes as the nitrene source, selectively generating α-methylene imines. Along with the scope of this reaction, mechanistic investigation, computational evidence, and further functionalization of these α-methylene imine products will be discussed.

Ring-opening oxidative amination of methylenecyclopropanes with diazenes via TiII/TiIV redox catalysis

255th National Meeting (2018)

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