Title
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
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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.
Keywords
LactonesOxidesRearrangementStereoselectivityTransition states
Object type
Language
English [eng]
Persistent identifier
https://phaidra.univie.ac.at/o:2090205
Appeared in
Title
Journal of the American Chemical Society
Volume
146
Issue
20
ISSN
0002-7863
Issued
2024
From page
13914
To page
13923
Publisher
American Chemical Society (ACS)
Date issued
2024
Access rights
Rights statement
© 2024 The Authors

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