Carbon–carbon bond formation reactions are of longstanding interest in organic chemistry. Improvements of the methods targeting its creation are still being performed, especially thanks to the development of innovative methodologies in transition metal catalysis and photocatalysis. This review will tackle the combination of transition metal and photoredox cycles to create carbon–carbon bonds, focusing on the four transition metals most reported in the literature in this domain: Ni, Pd, Au and Cu.

Biaryls have widespread applications in organic synthesis. However, sequentially polysubstituted biaryls are underdeveloped due to their challenging preparation. Herein, we report the synthesis of dissymetric 2,3,2′,3′,4-substituted biaryls via pericyclic reactions of cyclic diaryl λ3-bromanes. The functional groups tolerance and atom economy allow access to molecular complexity in a single reaction step. Continuous flow protocol has been designed for the scale-up of the reaction, while postfunctionalizations have been developed taking advantage of the residual Br-atom.