Abstract
The formation of C‐heteroatom bonds represents an important type of bond‐forming reaction in organic synthesis and often provides a fast and efficient access to privileged structures found in pharmaceuticals, agrochemical and materials. In contrast to conventional Pd‐ or Cu‐catalyzed C‐heteroatom cross‐couplings under high‐temperature conditions, recent advances in homo‐ and heterogeneous Ni‐catalyzed C‐heteroatom formations under mild conditions are particularly attractive from the standpoint of sustainability and practicability. The generation of NiIII and excited NiII intermediates facilitate the reductive elimination step to achieve mild cross‐couplings. This review provides an overview of the state‐of‐the‐art approaches for mild C‐heteroatom bond formations and highlights the developments in photoredox and nickel dual catalysis involving SET and energy transfer processes; photoexcited nickel catalysis; electro and nickel dual catalysis; heterogeneous photoredox and nickel dual catalysis involving graphitic carbon nitride (mpg‐CN), metal organic frameworks (MOFs) or semiconductor quantum dots (QDs); as well as more conventional zinc and nickel dual catalyzed reactions.
The generation of NiIII and excited NiII intermediates facilitates the reductive elimination step leading to the mild cross‐couplings. This review provides an overview of the state‐of‐the‐art approaches for mild C‐heteroatom bond formations via homo‐ and heterogeneous photoredox and nickel dual catalysis, electro‐ and nickel dual catalysis, as well as conventional zinc and nickel dual catalysis.