Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 4, Pages 1208-1212Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201809601
Keywords
electrostatic interactions; ion pairs; radicals; Stetter reaction; umpolung
Categories
Funding
- WWU Munster
- Deutsche Forschungsgemeinschaft [SFB858]
- Verband der Chemischen Industrie
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A bioinspired, intermolecular radical Stetter reaction of alpha-keto acids and aldehydes is disclosed that is contingent on a formal radical umpolung concept. Enabled by secondary amine activation, electrostatic recognition ensures that the alpha-ketocarboxylic acids, which function as latent acyl radicals, are proximal to the in situ generated iminium salts. This photoactive contact ion pair is an electron donor-acceptor (EDA) complex, and undergoes facile single electron transfer (SET) and rapid decarboxylation prior to radical-radical recombination. Importantly, decarbonylation is mitigated by this strategy. The initial computational validation on which the process is predicated matches closely with experiment. Synergising organo- and photocatalysis activation principles finally expands the mechanistic and synthetic scope of the classic Stetter reaction to include alpha,beta-unsaturated aldehydes as acceptors.
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