Supported Atomically Dispersed Pd Catalyzed Direct Alkoxylation and Allylic Alkylation†

Abstract

Comprehensive SummaryA new approach to allylic alkylation is realized using an atomically dispersed palladium catalyst (Pd1/TiO2‐EG). Unlike conventional methods that require derivation of substrates and utilization of additives, this method allows for direct allylic alkylation from allylic alcohols, producing H2O as the sole by‐product. The catalyst's high efficiency is attributed to the local hydrogen bonding at the organic‐inorganic interface (Pd‐EG interface), facilitating hydroxyl group activation for η3 π‐allyl complex formation. The system demonstrates successful direct C—O and C—C coupling reactions with high selectivity, requiring no additives. This study highlights the potential of supported atomically dispersed catalysts for greener and more efficient catalysis, meanwhile, offers unique insights into the distinct behavior of atomically dispersed catalysts in comparison to homogeneous or nanoparticle‐based catalysts.