What is the difference between mono- and biphosphine ligands? Revealing the chemoselectivity in Pd-catalysed carbenation of bromonaphthalene

Ligand-controlled chemoselectivity is an important topic in organometallic chemistry. In this work, DFT calculations were used to reveal the chemoselectivity of a Pd-catalysed three-component dearomative carbenation of bromonaphthalene with diazo compounds and allylborates. When a monophosphine ligand was used, ligand exchange with a diazo compound was favored by the release of a phosphine ligand. Therefore, a three-component coupling reaction could occur. However, when a biphosphine ligand was used, ligand exchange between the phosphine and the diazo compounds was difficult. Therefore, the Suzuki-Miyaura coupling product was observed in this case, without the participation of the carbene moiety.

Automated summary

This work used DFT calculations to reveal the chemoselectivity of a Pd-catalysed multi-component reaction by controlling ligand exchange. The choice of different ligands can control different chemical pathways in the reaction.