A site-selective amination catalyst discriminates between nearly identical C-H bonds of unsymmetrical disubstituted alkenes

C-H activation reactions enable chemists to unveil new retrosynthetic disconnections and streamline conventional synthetic approaches. A long-standing challenge in C-H activation is the inability to distinguish electronically and sterically similar C-H bonds. Although numerous synergistic combinations of transition-metal complexes and chelating directing groups have been utilized to distinguish C-H bonds, undirected regioselective C-H functionalization strategies remain elusive. Here we report a regioselective C-H activation/amination reaction of various unsymmetrical dialkyl-substituted alkenes. The regioselectivity of C-H activation is correlated to the electronic properties of allylic C-H bonds indicated by the corresponding(1)J(CH)coupling constants. A linear relationship between the difference in the (1)J(CH) coupling constants of the two competing allylic C-H bonds (Delta(1)J(CH)) and the C-H activation barriers (Delta Delta G double dagger) has also been determined.