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.

A mild approach for the decarboxylative aminomethylation of aryl sulfonates by the combination of photoredox and nickel catalysis through C-O bond cleavage is described for the first time. A wide range of aryl triflates as well as aryl mesylates, tosylates and alkenyl triflates afford the corresponding products in good to excellent yields.

Two efficient protocols for the nickel-catalyzed aryl-alkyl cross-coupling reactions using esters as coupling components have been established. The methods enable the selective oxidative addition of nickel to acyl C−O and aryl C−O bonds and allow the aryl-alkyl cross-coupling via decarbonylative bond cleavage or through cleavage of C−O bond with high efficiency and good functional group compatibility. The protocols allow the streamlined, unconventional utilization of widespread ester groups and their precursors, carboxylic acids and phenols in synthetic organic chemistry.

A new catalytic method for the direct alkylation of allylic C(sp3)–H bonds from unactivated alkenes via synergistic organo- and photoredox catalysis is described.