Recent progress in nickel-catalyzed carboboration of alkenes

Alkenes represent one of the most useful building blocks for organic synthesis, owing to their abundance and versatile reactivity. Transition metal (Pd, Cu, Co, Ni, Fe, etc.) catalyzed difunctionalization of alkenes provides efficient access to substituted molecules from readily available alkenes by installing functional groups across their carbon-carbon double bonds. Particularly, Nickel-based catalytic complexes have attracted a great deal of attention. This is because they are prone to undergoing oxidative addition and slow β-hydride elimination, and can access both two-electron and radical pathways. Numerous elegant Ni-catalyzed cross-coupling methods, e.g., (hetero)arylboration, alkenylboration, alkylboration and alkynylboration of alkenes, have been developed with broad scopes and a high tolerance to a variety of functional groups. Therefore, the Ni-catalyzed carboboration of alkenes has become an efficient synthetic protocol to deliver substituted compounds by the cross-coupling of alkenes, electrophiles, and B₂Pin₂. Despite this progress, a number of challenging issues remaining in the field include broadening the types of carboboration reactions, especially the asymmetric ones, diversifying electrophile types (which is limited to halogens for now) and gaining profound insight into the reaction mechanisms. This review summarizes the recent progress in this emerging field from the literature published since 2018. It will provide the scientific community with convenience to access collective information and to accelerate their further research in order to broaden the scope of methodology and application in drug discovery programs.