Recent progress on Ni-catalysed alkyl-alkyl cross-coupling enabled by asymmetric hydrofunctionalization of alkenes.

The construction of saturated stereogenic centers, which are of significance in cutting-edge fields such as pharmaceutical research and materials science, represents a fundamental objective in organic synthetic chemistry. In this context, nickel-catalysed hydroalkylation of alkenes has emerged as a promising strategy for efficient construction of chiral carbon centers by C(sp3)-C(sp3) cross-coupling with alkyl electrophiles. This reaction mode circumvents the use of stoichiometric alkyl metallic reagents, offering a new opportunity for the synthesis of chiral carbon centers by C(sp3)-C(sp3) coupling. By exploiting readily available alkenes as coupling partners, these transformations enable rapid molecular saturation with enantioselectivity control under mild conditions. This review systematically summarizes recent advances in Ni-catalysed alkyl-alkyl coupling enabled by hydroalkylation of alkenes, with an emphasis on strategy development, mechanistic elucidation, and synthetic applications. Despite notable progress, challenges remain in further expanding substrate scope, enhancing catalytic efficiency, and refining mechanistic understanding to advance the synthetic utility of this strategy.