Recent Progress on Nickel‐Catalyzed Reductive Dicarbofunctionalization of Alkenes ^†

Comprehensive Summary As readily available and abundant industrial feedstocks, alkenes have emerged as versatile platform for constructing value‐added targets. Transition metal‐catalyzed dicarbofunctionalizations reactions forge two carbon‐carbon bonds in one step with construction of two vicinal saturated carbon centers, providing profound synthetic potential in organic synthesis and pharmaceutical chemistry. In particular, nickel‐catalyzed reductive dicarbofunctionalization of alkenes has witnessed remarkable progress in recent years. Compared to conventional redox‐neutral dicarbofunctionalization strategy, reductive variant offers significant advantages, such as no use of pre‐formed organometallic reagents, operational simplicity and mild reaction conditions. This review summarizes developments of nickel‐catalyzed reductive dicarbofunctionalization of alkenes to forge diverse carbon‐carbon bonds in the absence of stoichiometric carbon nucleophiles. The mechanistic considerations are comprehensively discussed, including two‐electron migratory insertion and the single‐electron radical addition pathways. Furthermore, we provide critical insights into future directions and potential challenges in this area, highlighting opportunities for further methodology development and applications for nickel‐catalyzed reductive dicarbofunctionalization of alkenes. Key Scientists