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

Abstract Traditional homogeneous transition‐metal catalysts are unlikely applied for alkoxycarbonylation of higher olefins to produce value‐added esters due to the easily decomposition of phosphorus ligands under high separation temperatures. In this work, we evaluated a series of cheap and easily made heterogenized triphenylphosphine‐palladium catalysts via a polymerization concept for methoxylcarbonylation of C6–C12 higher olefins. Importantly, compared to the parent homogeneous catalyst Pd/PPh 3 , catalyst Pd/V‐PPh 3 @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, subtly tuned catalysts Pd/2V‐PPh 3 @POP, Pd/3V‐PPh 3 @POP, and Pd/ t Bu 2 PPh@POP where the monomers are installed with extra vinyl groups or a bulky tert ‐butyl group show significantly reduced linear selectivity (41.6%–64.0%) and highly promoted unwanted isomerization selectivity (10.5%–92.9%). Finally, catalysts Pd/V‐PPh 3 @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.