New insight into Cu-catalyzed borocarbonylative coupling reactions of alkenes with alkyl halides

Density functional theory (DFT) calculations were performed to better understand the mechanism of copper-catalyzed four-component borocarbonylative coupling of alkenes with alkyl halides by using bis(pinacolato)diboron as the boron reagent under CO atmosphere as reported in the recent literature. An unexpected reaction mechanism was shown to be viable, which occurs via a CuI-only involved, two-ligand relay-enabled, and no radical-participated copper catalysis with a SN2-type C-C coupling fashion. The theoretical results rationalized the experimentally observed regio- and chemoselectivities, and substituent effect of alkenes as well as the fact the reaction is totally inhibited by radical trapping reagents.

Automated summary

Density functional theory (DFT) calculations were performed to investigate the mechanism of copper-catalyzed four-component borocarbonylative coupling of alkenes with alkyl halides using bis(pinacolato)diboron as the boron reagent under CO atmosphere. The theoretical results revealed an unexpected reaction mechanism involving CuI as the sole catalyst, with a two-ligand relay mechanism and no radical participation, proceeding through SN2-type C-C coupling. The experimental observations of regio- and chemoselectivities, as well as the inhibition of the reaction by radical trapping reagents, were rationalized by the theoretical analysis.