Plasmonic Silver-Nanoparticle-Catalysed Hydrogen Abstraction from the C(sp3 )-H Bond of the Benzylic Cα atom for Cleavage of Alkyl Aryl Ether Bonds.
Angew Chem Int Ed Engl
; 62(4): e202215201, 2023 Jan 23.
Article
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| ID: mdl-36450692
ABSTRACT
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 Cα atom of an alkyl aryl ether ß-O-4 linkage. The intense electromagnetic near-field generated at the illuminated plasmonic NPs promotes chemisorption of the ß-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 Cß -O bond under moderate reaction conditions (≈90 °C). The plasmon-driven process has certain exceptional features enabling hydrogen abstraction from a specific C(sp3 )-H bond, along with precise scission of the targeted C-O bond to form aromatic compounds containing unsaturated, substituted groups in excellent yields.
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Colección:
01-internacional
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MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Año:
2023
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Article