Titanium Radical Redox Catalysis: Recent Innovations in Catalysts, Reactions, and Modes of Activation.

Radical chemistry has emerged as a cornerstone in modern organic synthesis, providing chemists with numerous new tools to rapidly expand reactivity and chemical space in academic and industrial research. In this regard, titanium complexes have been recognized as an attractive class of catalysts owing to their rich redox activities in addition to the abundance and low toxicity of this early transition metal. Traditionally employed for the activation of epoxides and carbonyl compounds, Ti radical redox catalysis has broken into new grounds in recent years, giving rise to a diverse repertoire of useful transformations. In this Perspective, we highlight recent developments in the area of TiIII/IV catalysis with respect to the activation of different types of chemical bonds. Furthermore, we discuss future opportunities in integrating Ti radical chemistry with other catalytic systems as well as with emerging new technologies such as photochemistry and electrochemistry.