Metal-free alkene oxy- and amino-perfluoroalkylations via carbocation formation by using perfluoro acid anhydrides: unique reactivity between styrenes and perfluoro diacyl peroxides

We present a strategy for metal-free, alkene difunctionalization-type, oxy- and amino-perfluoroalkylations, using perfluoro acid anhydrides as practical and user-friendly perfluoroalkyl sources. This method provides efficient access to oxy-perfluoroalkylation products carbocation formation due to th...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2018, Vol.9 (35), p.7115-7121
Main Authors: Valverde, Elena, Kawamura, Shintaro, Sekine, Daisuke, Sodeoka, Mikiko
Format: Article
Language:English
Subjects:
Acids
Anhydrides
Chemistry
Nucleophiles
Organic chemistry
Perfluoro compounds
Perfluoroalkyl & polyfluoroalkyl substances
Peroxides
Styrenes
Substitution reactions
User friendly products
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Summary:We present a strategy for metal-free, alkene difunctionalization-type, oxy- and amino-perfluoroalkylations, using perfluoro acid anhydrides as practical and user-friendly perfluoroalkyl sources. This method provides efficient access to oxy-perfluoroalkylation products carbocation formation due to the unique reactivity between styrenes and bis(perfluoroacyl) peroxides generated from perfluoro acid anhydrides. This reaction is also applicable to metal-free intramolecular amino-perfluoroalkylation of styrenes bearing a pendant amino group. Synthetic utility of the oxy-trifluoromethylation products was confirmed by demonstrating derivatization hydrolysis, elimination, and acid-catalyzed substitution with carbon nucleophiles. The mechanism of the carbocation formation was investigated experimentally and theoretically.
ISSN:2041-6520
2041-6539
DOI:10.1039/c8sc02547a