Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.1002/anie.201902785. Scheme 1. Homogeneous versus semi-heterogeneous dual Ni/photocatalysis. Angewandte Chemie Communications Angewandte Chemie Communications 9577 Angew.C hem. Int.E d. 2019, 58,9 575 -9580

A carbon nitride material can be combined with homogeneous nickel catalysts for light-mediated cross-couplings of aryl bromides with alcohols under mild conditions. The metal-free heterogeneous semiconductor is fully recyclable and couples a broad range of electron-poor aryl bromides with primary and secondary alcohols as well as water. The application for intramolecular reactions and the synthesis of active pharmaceutical ingredients was demonstrated. The catalytic protocol is applicable for the coupling of aryl iodides with thiols as well.

Photochemistry enables new synthetic means to form carbon–heteroatom bonds. Photocatalysts can catalyze carbon–heteroatom cross‐couplings by electron or energy transfer either alone or in combination with a second catalyst. Photocatalyst‐free methods are possible using photolabile substrates or by generating photoactive electron donor‐acceptor complexes. This review summarizes and discusses the strategies used in light‐mediated carbon–heteroatom bond formations based on the proposed mechanisms.