Titel
Stereodivergent Synthesis of 1,4-Dicarbonyl Compounds through Sulfonium Rearrangement: Mechanistic Investigation, Stereocontrolled Access to γ-Lactones and γ-Lactams, and Total Synthesis of Paraconic Acids
... show all
Abstract
Although simple γ-lactones and γ-lactams have received considerable attention from the synthetic community, particularly due to their relevance in biological and medicinal contexts, stereoselective synthetic approaches to more densely substituted derivatives remain scarce. The in-depth study presented herein, showcasing a straightforward method for the stereocontrolled synthesis of γ-lactones and γ-lactams, builds on and considerably expands the stereodivergent synthesis of 1,4-dicarbonyl compounds by a ynamide/vinyl sulfoxide coupling. A full mechanistic and computational study of the rearrangement was conducted, uncovering the role of all of the reaction components and providing a rationale for stereoselection. The broad applicability of the developed tools to streamlining synthesis is demonstrated by concise enantioselective total syntheses of (+)-nephrosteranic acid, (+)-rocellaric acid, and (+)-nephromopsinic acid.
Stichwort
LactonesOxidesRearrangementStereoselectivityTransition states
Objekt-Typ
Sprache
Englisch [eng]
Persistent identifier
Erschienen in
Titel
Journal of the American Chemical Society
Band
146
Ausgabe
20
ISSN
0002-7863
Erscheinungsdatum
2024
Seitenanfang
13914
Seitenende
13923
Publication
American Chemical Society (ACS)
Erscheinungsdatum
2024
Zugänglichkeit
Rechte
Rechteangabe
© 2024 The Authors
Universität Wien | Universitätsring 1 | 1010 Wien | T
+43-1-4277-0