Confined Trinuclear Ru Sites in Phosphine-Incorporated Porous Organic Polymers for the Direct Synthesis of Alcohols from Reductive Hydroformylation of Alkenes

Direct conversion of readily available alkenes into high-value-added alcohols is important yet challenging in both organic synthesis and industry. One-pot reductive hydroformylation of alkenes offers a straightforward and atom-economical method for the synthesis of one-carbon homologated alcohols. However, the reaction catalyzed by a stable and efficient heterogeneous catalyst has been underexplored. Herein, we report a bench-stable porous organic polymer (POP) with incorporation of a specific monophosphine ligand into the scaffold, which serves as both a solid ligand and a support to prepare a heterogeneous Ru catalyst for one-pot reductive hydroformylation. The monophosphine ligand helps to stabilize atomically dispersed trinuclear Ru sites on POP, resulting in a heterogeneous Ru catalyst with a catalytic performance comparable to its homogeneous counterpart under the same conditions. The catalyst could be easily separated for successive reuses without a significant loss in both activity and selectivity. Remarkably, the catalyst exhibited outstanding chemo- and regioselectivity, allowing for the efficient conversion of a wide range of terminal, internal, and functional alkenes to their respective alcohols in good to high yields. This work demonstrates the use of atomically dispersed metal sites for the reductive hydroformylation of alkenes for the direct synthesis of alcohols.