Heterogeneous single-site catalysts can combine the precise active site design of organometallic complexes with the efficient recovery of solid catalysts. Based on recent progress on homogeneous thioether ligands for Pd-catalyzed C-H activation reactions, we here develop a scalable MOF-based heterogeneous single-site catalyst containing S,O-moieties that increase the catalytic activity of Pd(II) for the oxidative alkenylation of arenes. The structure of the Pd@MOF-808-L1 catalyst was characterized in detail via solid-state nuclear magnetic resonance spectroscopy, N2 physisorption, and high angle annular dark field scanning transmission electron microscopy, and the structure of the isolated palladium active sites could be identified by X-ray absorption spectroscopy. A turnover frequency (TOF) of 8.4 h -1 was reached after 1 h reaction time, which was three times higher than the TOF of standard Pd(OAc)2, ranking Pd@MOF-808-L1 among the most active heterogeneous catalysts ever reported for the non-directed oxidative alkenylation of arenes. Finally, we showed that the single-site catalyst promotes the oxidative alkenylation of a broad range of electron-rich arenes, and the applicability of this heterogeneous system was demonstrated by the gram-scale synthesis of industrially relevant products.

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 significant challenges with regard to atom economy and practicality. Herein we show a new approach that harnesses the shape-selective and catalytic properties of zeolites to drive the shuttling equilibrium to near-completion. This strategy is demonstrated for transfer hydrocyanation and transfer hydroformylation reactions, showing yield increases up to 80% by the addition of a carefully selected zeolite. Clear improvements such as diversification of HCN-donors to e.g. propionitrile and the use of a simple reaction setup with mild conditions are achieved. The use of unstrained and unactivated olefins as HCHO-acceptors is demonstrated for the first time, significantly broadening the scope and utility of the transfer hydroformylation reaction. Mechanistic and spectroscopic studies highlight the unique synergy between the zeolites and the homogeneous transfer catalysts.

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 signi cant challenges with regard to atom economy and practicality. Herein we show a new approach that harnesses the shape-selective and catalytic properties of zeolites to drive the shuttling equilibrium to near-completion. This strategy is demonstrated for transfer hydrocyanation and transfer hydroformylation reactions, showing yield increases up to 80% by the addition of a carefully selected zeolite. Clear improvements such as diversi cation of HCN-donors to e.g. propionitrile and the use of a simple reaction setup with mild conditions are achieved. The use of unstrained and unactivated ole ns as HCHO-acceptors is demonstrated for the rst time, signi cantly broadening the scope and utility of the transfer hydroformylation reaction. Mechanistic and spectroscopic studies highlight the unique synergy between the zeolites and the homogeneous transfer catalysts.