Recently, several new Ti-catalyzed oxidative nitrene transfer reactions have been reported that proceed through a purported Ti(II)/Ti(IV) redox cycle. In this submission, our initial mechanistic investigations into these unique transformations will be discussed. Remarkably, these Ti redox catalytic events are broadly accessible across a range of Ti structures, although the rates and selectivity of catalysis can vary widely. These mechanistic studies will be used to rationalize new methods for controlling the selectivity over several Ti-catalyzed nitrene transfer reactions, including the [2+2+1] synthesis of pyrroles from alkynes and diazenes and the oxidative multicomponent carboamination of alkynes with diazenes and alkenes.

Studies on the mechanism of Ti-catalyzed nitrene transfer reactions

253rd National Meeting (2017)

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