Ti-Catalyzed Nitrene Transfer Reactions: A Platform for Fundamental Reaction Discovery and Exploration

Titanium is an ideal metal for green and sustainable catalysis—it is the 2^nd most earth-abundant transition metal, and the byproducts of Ti reactions (typically 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. Several years ago our group discovered that Ti imidos (L_nTi=NR) can catalyze oxidative nitrene transfer reactions from diazenes via a Ti^II/Ti^IV redox couple. We are using this new mode of reactivity to develop a large suite of practical synthetic methods. In this talk, our latest synthetic and mechanistic discoveries related to Ti nitrene transfer catalysis and other amination reactions will be discussed, including new catalyst design strategies for selective construction of pyrroles via [2+2+1] cycloaddition of alkynes with Ti nitrenes and alkynes, as well as new methods for catalytic oxidative amination, multicomponent N-N oxidative coupling to synthesize pyrazoles, and more. Additionally, a case study using iterative supervised principal component analysis (ISPCA), a new statistical tool for predictive catalysis, will be showcased in the context of selective pyrrole synthesis.

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