LiCl‐Promoted Branched Methoxycarbonylation of Propylene Using a Heterogenized Triphenylphosphine‐palladium Catalyst

Abstract Branched selective carbonylation of propylene is a well‐known challenge for both academia and industry. In this study, we reported LiCl‐promoted branched selective methoxycarbonylation of propylene utilizing an easy heterogenized triphenylphosphine‐palladium catalyst (Pd/3V‐PPh 3 @POP). Various (heterogenized) ligands, additives, acids, and catalytic metals were tested. The catalyst Pd/3V‐PPh 3 @POP in the presence of LiCl gave a 36.9% increased branched selectivity at the expense of activity compared to the absence of additives (71.4% versus 34.5% branched selectivity, turnover numbers of 124.5 versus 421.8) under otherwise identical conditions. The optimal catalyst Pd/3V‐PPh 3 @POP was characterized using X‐ray diffraction (XRD), high‐angle annular dark field scanning transmission electron microscopy (HAADF‐STEM), scanning electron microscopy energy dispersive spectrometer (SEM‐EDS), Brunner–Emmet–Teller (BET), and thermogravimetric analysis (TGA) experiments and further tested in simple filtration recycling experiments using a continuous stirring reactor.