Examination of Heterogenized Triphenylphosphine‐Palladium‐Catalysts for Methoxycarbonylation of Higher Olefins

Traditional homogeneous transition‐metal‐catalysts are unlikely applied for alkoxycarbonylation of higher olefins to produce value‐added esters due to easily decomposition of phosphorus ligands under high separation temperatures. Herein, we evaluated a series of cheap and easy‐made heterogenized triphenylphosphine‐palladium‐catalysts via a polymerization concept for methoxylcarbonylation of C6‐C12 higher olefins. Importantly, compared to the parent homogeneous catalyst Pd/PPh3, catalyst Pd/V‐PPh3@POP with an amorphous structure and homogeneously supported Pd metals shows improved linear selectivity in methoxycarbonylation of 1‐octene (79.2% vs. 75.6%) and as well can be easily separated from the reaction mixture by simple filtration for reusage under optimized conditions. Furthermore, subtle tuned catalysts Pd/2V‐PPh3@POP, Pd/3V‐PPh3@POP and Pd/tBu2PPh@POP where the monomers are installed with extra vinyl groups or a bulky tert‐butyl group shows significantly reduced linear selectivity (41.6‐64.0%) and highly promoted unwanted isomerization selectivity (10.5‐92.9%). Finally, catalyst Pd/V‐PPh3@POP are used for linear selectively converting of 1‐hexane (75.6%), methyl 10‐undecanoate (76.2%), diisobutylene (99.9%) and as well extremely challenging styrene (75.6%) to produce valuable linear esters.