Mechanistic study of CuH-catalyzed hydroarylation of alkenes with polyfluoroarenes involving C-F bond functionalization: noncovalent interaction-controlled regioselectivity

There is ongoing interest in catalysis with the earth-abundant metal copper (Cu). This density functional theory (DFT) study explores the detailed workings of the first CuH-catalyzed hydroarylation of alkenes with polyfluoroarenes involving C-F bond functionalization. The CuH complex undergoes Markovnikov hydrocupration with the aryl alkene substrate to give a Cu(i) benzyl intermediate, and the regioselectivity is due to a combination of orbital and dispersion interactions induced by the aryl alkene substrate. The benzyl ligand allows a 1,3-cupratropic shift for the Cu(i) complex to have an exposed carbonanionic atom facilitating nucleophilic aromatic substitution to the polyfluoroarene substrate. The distinct regioselectivity of para-C-F substitution is controlled by the noncovalent C(sp³)-H/π and C(sp²)-H⋯O interactions. These mechanistic insights can have implications for the development of new transition metal-catalyzed hydroarylation and C-F functionalization reactions.