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Radical Arylation of Anilines and Pyrroles via Aryldiazotates
Author(s) -
Hofmann Josefa,
Gans Eva,
Clark Timothy,
Heinrich Markus R.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701429
Subject(s) - homolysis , regioselectivity , chemistry , aqueous solution , aryl , aryl radical , catalysis , radical ion , radical , transition metal , photochemistry , ion , combinatorial chemistry , organic chemistry , alkyl
The radical arylation of anilines and pyrroles can be achieved under transition‐metal‐ and catalyst‐free conditions by using aryldiazotates in strongly alkaline aqueous solutions. The aryldiazotates act as protected diazonium ions, which do not undergo azo coupling with electron‐rich aromatic substrates, but can still serve as an aryl radical source at slightly elevated temperatures. Based on an improved preparation of aryldiazotates in aqueous solution, homolytic aromatic substitutions of anilines and pyrroles were conducted with good overall yields and high regioselectivity. Moreover, DFT calculations provided further mechanistic insights.