Palladium complexes of abnormal N-heterocyclic carbenes as precatalysts for the much preferred Cu-free and amine-free Sonogashira coupling in air in a mixed-aqueous medium

Abstract

A series of new PEPPSI (Pyridine Enhanced Precatalyst Preparation Stabilization and Initiation) themed precatalysts of abnormal N-heterocyclic carbenes for the highly desirable Cu-free and amine-free Sonogashira coupling in air in a mixed-aqueous medium is reported. Specifically, the PEPPSI themed (NHC)PdI₂(pyridine) type precatalysts, 1b–4b, efficiently carried out the highly convenient Cu-free and amine-free Sonogashira coupling of aryl bromides and iodides with terminal acetylenes in air in a mixed aqueous medium. Complexes, 1b–4b, were synthesized by the direct reaction of the corresponding imidazo[1,2-a]pyridinium iodide salts, 1a–4a, with PdCl₂ in pyridine in the presence of K₂CO₃ as a base while the imidazo[1,2-a]pyridinium iodide salts, 1a–4a, were in turn synthesized by the alkylation reactions of the respective imidazo[1,2-a]pyridine derivatives with alkyl iodides. The density functional theory (DFT) studies revealed that these imidazol-3-ylidene[1,2-a]pyridine derived abnormal carbenes are strongly σ-donating and consequently significantly weaken the catalytically important labile trans pyridine ligand in 1b–4b.