Plasmonic Silver‐Nanoparticle‐Catalysed Hydrogen Abstraction from the C( <i>sp</i> ^<i>3</i> )−H Bond of the Benzylic C _α atom for Cleavage of Alkyl Aryl Ether Bonds

Selective activation of the C(sp3)−H bond is an important process in organic synthesis, where efficiently activating a specific without causing side reactions remains one chemistry's great challenges. Here we report that illuminated plasmonic silver metal nanoparticles (NPs) can abstract hydrogen from Cα atom alkyl aryl ether β-O-4 linkage. The intense electromagnetic near-field generated at NPs promotes chemisorption compound and transfer photo-generated hot electrons to adsorbed molecules leads abstraction direct cleavage unreactive Cβ−O under moderate reaction conditions (≈90 °C). plasmon-driven has certain exceptional features: enabling bond, along with precise scission targeted C−O form aromatic compounds containing unsaturated, substituted groups excellent yields.