biostudies-literatureHan PPostdoctoral Research Foundation of ChinaNational Natural Science Foundation of ChinaAustralian Research Councile202215201https://www.ebi.ac.uk/biostudies/studies/S-EPMC10108273biostudies-literatureUnknown62(4)Selective activation of the C(sp³ )-H bond is an important process in organic synthesis, where efficiently activating a specific C(sp³ )-H bond without causing side reactions remains one of chemistry's great challenges. Here we report that illuminated plasmonic silver metal nanoparticles (NPs) can abstract hydrogen from the C(sp³ )-H bond of the C_α atom of an alkyl aryl ether β-O-4 linkage. The intense electromagnetic near-field generated at the illuminated plasmonic NPs promotes chemisorption of the β-O-4 compound and the transfer of photo-generated hot electrons from the NPs to the adsorbed molecules leads to hydrogen abstraction and direct cleavage of the unreactive ether C_β -O bond under moderate reaction conditions (≈90 °C). The pAngewandte Chemie (International ed. in English)Plasmonic Silver-Nanoparticle-Catalysed Hydrogen Abstraction from the C(sp³ )-H Bond of the Benzylic C_α atom for Cleavage of Alkyl Aryl Ether Bonds.PMC101082732019M662760No. 22002038DP210103357DP200102652DE190101450Bottle SEHan PDu AMao XZhu HYSarina SWaclawik ERJin YJia JZhao JCfalsePlasmonic Silver-Nanoparticle-Catalysed Hydrogen Abstraction from the C(sp³ )-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 C(sp³ )-H bond without causing side reactions remains one of chemistry's great challenges. Here we report that illuminated plasmonic silver metal nanoparticles (NPs) can abstract hydrogen from the C(sp³ )-H bond of the C_α atom of an alkyl aryl ether β-O-4 linkage. The intense electromagnetic near-field generated at the illuminated plasmonic NPs promotes chemisorption of the β-O-4 compound and the transfer of photo-generated hot electrons from the NPs to the adsorbed molecules leads to hydrogen abstraction and direct cleavage of the unreactive ether C_β -O bond under moderate reaction conditions (≈90 °C). The p2023-01-01T00:00:00Z2023 Jan2025-04-26T04:59:12.332Z2025-04-06T11:23:05.317ZS-EPMC101082733645069210.1002/anie.202215201