Xantphos-derived porous polymer: a robust solid-state ligand for efficient Pd-catalyzed alkoxycarbonylation of alkenes from mono-alcohols to polyols

The integration of superior homogeneous catalytic activity with the practical advantages of facile separation and robust recyclability of heterogeneous systems remains a grand challenge. Here, we report a heterogenized bidentate phosphine ligand, constructed by integrating commercial Xantphos into a hypercrosslinked porous polymer, as a versatile platform for Pd-catalyzed alkoxycarbonylation. The tailored polymer, featuring a high surface area, hierarchical pores, and chemical robustness, provides privileged coordination microenvironments. It empowers highly efficient alkoxycarbonylation of diverse alkenes with various alcohols, including monoalcohols, diols, and polyols, to produce valuable esters with activity and selectivity comparable to its homogeneous molecular counterpart. Moreover, the catalytic system enables the in-situ formation of a robust Pd catalyst, wherein Pd nanoparticles are stabilized and uniformly dispersed via strong Pd-P coordination. This resulting catalyst demonstrates exceptional durability, being readily recycled over ten times without significant degradation in performance. This work pioneers a versatile platform for ligand immobilization that effectively bridges homogeneous efficiency with heterogeneous durability, unlocking efficient and sustainable pathways for carbonylation and other ligand-mediate transformations.