Ligand-controlled regiodivergent Ni-catalyzed trans-hydroboration/carboboration of internal alkynes with B2pin2

Unprecedented regioselective trans-hydroboration and carboboration of unbiased electronically internal alkynes were realized via a nickel catalysis system with the aid of the directing group strategy. Furthermore, the excellent alpha- and beta-regioselectivity could be accurately switched by the nitrogen ligand (terpy) and phosphine ligand (Xantphos). Mechanistic studies provided an insight into the rational reaction process, that underwent the cis-to-trans isomerization of alkenyl nickel species. This transformation not only expands the scope of transition-metal-catalyzed boration of internal alkynes but also, more particularly, portrays the vast prospects of the directing group strategy in the selective functionalization of unactivated alkynes.