Titanium is an ideal metal for green and sustainable catalysis—it is the 2nd most earth-abundant transition metal, and the byproducts of Ti reactions (TiO2) are nontoxic. However, a significant challenge of utilizing early transition metals for catalytic redox processes is that they typically do not undergo facile oxidation state changes because of the thermodynamic stability of their high oxidation states. We have recently discovered that Ti imidos (LnTi=NR) can catalyze oxidative nitrene transfer reactions from diazenes via a TiII/TiIV redox couple, and are using this new mode of reactivity to develop a large suite of practical synthetic methods. In this talk, our latest results related to selective heterocycle synthesis and oxidative carbene transfer will be discussed in the context of our current understanding of the broader mechanistic implications of Ti redox catalysis. A central theme of each of these reactions is that involvement of the pi system of the substrates and products is critical for productive Ti redox catalysis to occur.

Ti-catalyzed nitrene transfer reactions: Harnessing the TiII/TiIV redox couple for new transformations

2019 Fall National Meeting

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