In 2022,Ghosh, Boyli; Banerjee, Ambar; Roy, Lisa; Manna, Rabindra Nath; Nath, Rounak; Paul, Ankan published an article in Angewandte Chemie, International Edition. The title of the article was 《The Role of Copper Salts and O2 in the Mechanism of C≃N Bond Activation for Facilitating Nitrogen Transfer Reactions》.Synthetic Route of Br2Cu The author mentioned the following in the article:
CN bond scission can be a potential avenue for the functionalization of chem. bonds. We have conducted a computational study, using d. functional theory (DFT) and ab initio multireference CASSCF methods, to unravel the intricate mechanistic pathways traversed in the copper-promoted, dioxygen-assisted reaction for the formation of aryl isocyanate species from aryl aldehyde. This aryl isocyanate species acts as an active species for CN bond cleavage of coordinated cyanide anion enabling nitrogen transfer to various aldehydes. Electronic structure anal. revealed that under all the reaction conditions radical-based pathways are operative, which is in agreement with the exptl. findings. The major driving force is a CuII/I redox cycle initiated by single-electron transfer from the carbon center of the nitrile moiety. Our study reveals that the copper salts act as the “”electron pool”” in this unique nitrogen transfer reaction forming an aryl isocyanate species from aryl aldehydes. In addition to this study using Cupric bromide, there are many other studies that have used Cupric bromide(cas: 7789-45-9Synthetic Route of Br2Cu) was used in this study.
Some reported applications of Cupric bromide(cas: 7789-45-9) are: catalyst in cross coupling reactions; co-catalyst in Sonogashira coupling; lewis acid in enantioselective addition of alkynes.Synthetic Route of Br2Cu
Referemce:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”