Irradiation of Cp2TiCl2 with green light leads to electronically excited [Cp2TiCl2]*. This complex constitutes an efficient photoredox catalyst for the reduction of epoxides and for 5‐exo cyclizations of suitably unsaturated epoxides. To the best of our knowledge, our system is the first example of a molecular titanium photoredox catalyst.

Irradiation of Cp 2 TiCl 2 with green light leads to electronically excited [Cp 2 TiCl 2 ]*. This complex constitutes an efficient photoredox catalyst for the reduction of epoxides and for 5-exo cyclizations of suitably unsaturated epoxides. To the best of our knowledge, our system is the first example of a molecular titanium photoredox catalyst.

We describe a regiodivergent synthesis of pseudo‐C2‐symmetrical and pseudo‐meso bis‐indoline scaffolds from norbornadiene and substituted o‐iodo‐anilines. The Pd(0)/Josiphos system enables the highly regioselective catalyst controlled carboaminations required for the two step synthesis of the scaffolds.