Nickel-catalyzed reductive arylalkylation of alkenes: 5-exo cyclization vs. 6-endo cyclization vs. 1,2-aryl migration to 6-endo product

The detailed mechanisms of Ni-catalyzed reductive arylalkylation of unactivated alkenes with aryl bromides to synthesize benzene-fused 5-exo and 6-endo cyclic compounds were systematically investigated by DFT calculations. Our finding reveals that, under the catalysis of a Ni/biOx system with Zn as a reductant, bromobenzene containing a terminal olefin unit preferentially undergoes traditional Heck cyclization and cross-coupling reactions, favoring the formation of 5-exo cyclization products. In contrast, when Zn is absent, NiIII-alkyl species play a pivotal role, facilitating a rare 1,2-aryl migration followed by H-atom abstration, which selectively yields 6-endo cyclization products.