Visible-light-driven graphene supported Cu/Pd alloy nanoparticle-catalyzed borylation of alkyl bromides and chlorides in air.

A photocatalytic borylation of alkyl bromides and chlorides in air under visible-light irradiation by graphene-supported Cu-Pd alloy nanoparticles is reported. [Display omitted] • An efficient photocatalytic protocol for borylation of alkyl halides is reported. • A graphene supported Cu/Pd alloy nanoparticles was employed as photocatalyst. • The borylations were conducted at 30 °C in air under visible light. • Primary and secondary alkyl bromides and chlorides were borylated in good yields. • The high activity results from LSPR of Cu and alloy surface charge heterogeneity. A highly efficient photocatalytic protocol for borylation of alkyl bromides and chlorides with graphene supported Cu/Pd alloy nanoparticles as a heterogeneous catalyst is reported. This photocatalytic system operates with visible light in air, providing a wide range of primary and secondary alkyl halides with B 2 pin 2 or B 2 neop 2 in high yields at low temperatures, thereby demonstrating its broad utility and functional group tolerance. The high performance is attributed to a synergistic effect of localized surface plasmon resonance (LSPR) of Cu and charge transfer from Cu to Pd due to the alloy surface charge heterogeneity. Transfer of energetic electrons from Pd to electrophilic alkyl halides lead to the formation of the alkyl radicals, which quickly react with a nucleophilic adduct of a diboron compound with base adsorbed on the positively charged Cu sites to form the corresponding borylation product. [ABSTRACT FROM AUTHOR]