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Antagonistic Effect of Acetates in C–N Bond Formation with In Situ Generated Diazonium Salts: A Combined Theoretical and Experimental Study
Author(s) -
Fabre Indira,
Perego Luca Alessandro,
Bergès Julien,
Ciofini Ilaria,
Grimaud Laurence,
Taillefer Marc
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201600891
Subject(s) - chemistry , triazene , nucleophile , imidazole , reactivity (psychology) , pyrazole , reaction mechanism , redox , copper , decomposition , base (topology) , in situ , pyrrole , diazonium compounds , medicinal chemistry , combinatorial chemistry , polymer chemistry , organic chemistry , photochemistry , catalysis , medicine , mathematical analysis , alternative medicine , mathematics , pathology
The mechanism of the copper‐catalyzed arylation of nitrogen heterocycles using anilines via diazonium salts has been studied by combining DFT and experimental data. A Cu I /Cu III redox mechanism is proposed. Our study has revealed the multiple roles of the acid/base couple AcOH/AcO – . An in situ formed triazene species maintains a low concentration of diazonium salts in the reaction medium, which ensures limited formation of decomposition products. The results of DFT calculations have explained the lower reactivity of imidazole nucleophiles as compared with pyrazole in the arylation reaction.