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Published on: June 23, 2019
Radical Arylation of Anilines and Pyrroles via Aryldiazotates
Josefa Hofmann1, Eva Gans1, Timothy Clark2
1Department of Chemistry and Pharmacy, Pharmaceutical Chemistry, Friedrich-Alexander Universität Erlangen-Nürnberg, Schuhstraße 19, 91052, Erlangen, Germany.
Abstract:
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.
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