Atomically dispersed Rh sites with hemilabile coordination enables long-term stable and highly regioselective hydroformylation of allyl acetate

Developing heterogeneous Rh catalysts with high stability and anti-leaching properties for hydroformylation remains a long-standing challenge. In this work, we present a bidentate Xantphos-functionalized hypercrosslinked porous polymer with a large specific surface area and hierarchical pore structure, serving as both a heterogeneous ligand and support to construct a durable single-Rh-site catalyst. The single-Rh sites are confined within the crosslinked polymer framework through Rh P bond coordination, forming a unique hemilabile Rh structure, which exhibits outstanding catalytic performance in the hydroformylation of challenging functionalized allyl acetate. The catalyst achieved an unprecedented chemoselectivity of 95.4% and a regioselectivity of 318/1 toward 4-oxybutyl acetate, substantially outperforming those previously reported catalysts. It also demonstrates broad applicability by efficiently converting diverse olefins into the corresponding C +1 aldehyde with high yields. Notably, the catalyst retains high stability over 10 recycling in batches and 700 h of continuous-flow operation without observable performance decay or Rh leaching. This work offers a practical strategy for regioselective hydroformylation of functionalized alkenes and establishes a design framework for robust single-site heterogeneous catalysts in demanding carbonylative transformations.