Tuning the redox properties of the titanocene(III)/(IV)-couple for atom-economical catalysis in single electron steps.

Radical-based transformations are an attractive target for the development of catalytic processes due to ease of radical generation, high functional group tolerance and selectivity of bond-forming reactions. In spite of these appealing features, the potential of radicals as key intermediates in catalysis remains largely untapped. Herein we present recent work that exploits the innate ability of titanocene-based catalysts to undergo both oxidative addition and reductive elimination in single electron steps. We further demonstrate that tuning the redox properties of the titanocene-based catalyst can be used to develop efficient catalytic free radical processes including tetrahydrofuran synthesis, and radical arylation.