Recent Progress in NiH-Catalyzed Linear or Branch Hydrofunctionalization of Terminal or Internal Alkenes

The construction of C–C and C–X (X = N, O, Si, etc.) bonds is an important field in organic synthesis and methodology. In recent decades, studies on transition metal-catalyzed functionalization of alkenes have been on the rise. The individual properties of different transition metals determine the type of reaction that can be applied. Generally, post-transition metals with a large number of electrons in the d-orbit such as Mn, Fe, Co, Ni, Cu and Zn, etc., can be applied to more reaction types than pre-transition metals with a small number of electrons (e.g., Ti, Zr, etc.). Alkyl nickel intermediates formed by oxidative addition could couple with various of nucleophiles or electrophiles. Moreover, nickel has several oxidation valence states, which can flexibly realize a variety of catalytic cycles. These characteristics make nickel favored by researchers in the field of functionalization of alkenes, especially for the hydrofunctionalization of alkenes. Both terminal and internal alkenes could be converted, and the strategies of synthesizing linear and branched compounds have been expanded. Moreover, the guiding groups in alkenes played an almost decisive role in the regional selectivity, and the ligand or temperature also had regulating effects. Herein, we will give a comprehensive and timely overview of the works about the Ni-catalyzed hydrofunctionalization of alkenes and some insights on regional selectivity.

Graphic Abstract