Gold(I)‐Catalyzed N‐Desulfonylative Amination versus N‐to‐O 1, 5‐Sulfonyl Migration: A Versatile Approach to 1‐Azabicycloalkanes. (16th June 2016)

• Record Type: Journal Article
• Authors: Miaskiewicz, Solène; Gaillard, Boris; Kern, Nicolas; Weibel, Jean‐Marc; Pale, Patrick; Blanc, Aurélien
• Is Part Of: Angewandte Chemie. Volume 128:Number 31(2016)
• Page Start: 9234
• Page End: 9238
• Publication Date: 2016-06-16
• Subjects: Desulfonylierung -- Gold -- Homogene Katalyse -- N-Heterocyclen -- Sulfonyl-Migration; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201604329
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Valuable 1‐azabicycloalkane derivatives have been synthesized through a novel gold(I)‐catalyzed desulfonylative cyclization strategy. An ammoniumation reaction of ynones substituted at the 1‐position with an N ‐sulfonyl azacycle took place in the presence of a gold cation by intramolecular cyclization of the disubstituted sulfonamide moiety onto the triple bond. Depending on the size of the heterocyclic ring and substitution of the substrates, two unprecedented forms of nucleophilic attack on the sulfonyl group were exploited, that is, a N‐desulfonylation in the presence of an external protic O nucleophile (37–87 %, 10 examples) and a unique N‐to‐O 1, 5‐sulfonyl migration (60–98 %, 9 examples).