Premium
Acid‐Catalyzed Oxidative Radical Addition of Ketones to Olefins
Author(s) -
SchweitzerChaput Bertrand,
Demaerel Joachim,
Engler Hauke,
Klussmann Martin
Publication year - 2014
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.201401062
Subject(s) - chemistry , ketone , radical , catalysis , organic chemistry , alkyl , brønsted–lowry acid–base theory , oxidative phosphorylation , pyrrole , primary (astronomy) , biochemistry , physics , astronomy
Based on a mechanistic study, we have discovered a Brønsted acid catalyzed formation of ketone radicals. This is believed to proceed via thermally labile alkenyl peroxides formed in situ from ketones and hydroperoxides. The discovery could be utilized to develop a multicomponent radical addition of unactivated ketones and tert‐butyl hydroperoxide to olefins. The resulting γ‐peroxyketones are synthetically useful intermediates that can be further transformed into 1,4‐diketones, homoaldol products, and alkyl ketones. A one‐pot reaction yielding a pharmaceutically active pyrrole is also described.