Boosting the activity of Mizoroki–Heck cross-coupling reactions with a supramolecular palladium catalyst favouring remote Zn⋯pyridine interactions

Abstract

Transition metal catalysis benefitting from supramolecular interactions in the secondary coordination sphere in order to pre-organize substrates around the active site and reach a specific selectivity typically occur under long...

Repurposing a supramolecular iridium catalyst via secondary Zn⋯OC weak interactions between the ligand and substrate leads to ortho-selective C(sp2)–H borylation of benzamides with unusual kinetics

“…In other words, the highly sterically congested supramolecular iridium catalysts derived from ligands L1–L6 give no choice to the benzamide substrate than engaging in a Zn⋯OC weak interaction upon approaching the catalyst. In addition, similar to our previous observations using pyridines as substrates in metal catalysis, 18,23 such a supramolecular effect was completely lost in the presence of polar coordinating solvents such as THF, DMF or 1,4-dioxane, which disrupt the remote Zn⋯OC weak interaction by solvent-coordination to the zinc centre of the porphyrin backbone via Zn⋯O interaction. Aside from the key substrate-preorganization effects, increasing the effective molarity of the substrate around the catalyst is also a major advantage of the supramolecular iridium catalysts derived from L1–L6 .…”

Shortening CN⋯Br–Csp3 halogen bonds via π-stacking

“…During the course of our studies in the development of supramolecular catalysis, 20 we synthesized and obtained single crystals suitable for X-ray diffraction studies of 1 (Fig. 1).…”