Zeolites as equilibrium-shifting agents in shuttle catalysis

The catalytic shuttling of functional moieties has emerged as a promising strategy to substitute and diversify traditional hydrofunctionalization technologies. However, these reactions are reversible due to their isodesmic nature, which limits their applicability to a select array of donor and acceptor molecules, and poses substantial challenges with regard to atom economy and practicality. Here we show an approach that harnesses the shape-selective and catalytic properties of zeolites to drive the shuttling equilibrium of transfer hydrocyanation and transfer hydroformylation reactions to near-completion. The zeolites irreversibly convert the transfer reaction co-products in an exergonic tandem reaction while excluding the substrates via pore size restrictions. Through fine-tuning of the zeolite’s properties, yield increases of up to 80% can be achieved, enabling diversification of nitrile donors to propionitrile and aldehyde acceptors to unactivated olefins. Mechanistic and spectroscopic studies highlight the unique synergy between the zeolites and the homogeneous transfer catalysts. Shuttle catalysis is a promising approach to improve traditional hydrofunctionalization reactions, although thermodynamic constraints limit its application. Here the authors show how the properties of zeolites can drive the shuttling equilibrium of such catalytic processes, widening the applicability of reactions such as transfer hydrocyanation and transfer hydroformylation.