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Metal‐Free Carbonylations by Photoredox Catalysis
Author(s) -
Majek Michal,
Jacobi von Wangelin Axel
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201408516
Subject(s) - chemistry , electrophile , catalysis , carbonylation , benzoates , photoredox catalysis , carbon monoxide , aryl , redox , transition metal , eosin y , ligand (biochemistry) , photochemistry , alkyl , stoichiometry , combinatorial chemistry , organic chemistry , photocatalysis , biochemistry , receptor
The synthesis of benzoates from aryl electrophiles and carbon monoxide is a prime example of a transition‐metal‐catalyzed carbonylation reaction which is widely applied in research and industrial processes. Such reactions proceed in the presence of Pd or Ni catalysts, suitable ligands, and stoichiometric bases. We have developed an alternative procedure that is free of any metal, ligand, and base. The method involves a redox reaction driven by visible light and catalyzed by eosin Y which affords alkyl benzoates from arene diazonium salts, carbon monoxide, and alcohols under mild conditions. Tertiary esters can also be prepared in high yields. DFT calculations and radical trapping experiments support a catalytic photoredox pathway without the requirement for sacrificial redox partners.