Approach to Fully Substituted Cyclic Nitrones from N‐Hydroxylactam Derivatives: Development and Application to the Total Synthesis of Cylindricine C

An approach to cyclic nitrones from N‐hydroxylactam derivatives is documented. The nucleophilic addition of an organolithium reagent to an N‐OSEM [SEM=2‐(trimethylsilyl)ethoxymethyl] lactam forms a five‐membered chelated intermediate, which undergoes both elimination and deprotection to give a fully...

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Bibliographic Details
Published in:Angewandte Chemie 2019-03, Vol.131 (13), p.4425-4429
Main Authors: Hiraoka, Shobu, Matsumoto, Tsutomu, Matsuzaka, Koki, Sato, Takaaki, Chida, Noritaka
Format: Article
Language:English
Subjects:
Amide
Amides
Chemistry
Derivatives
Nitrone
Nukleophile Addition
Oxidation
Reagents
Substitutes
Synthesemethoden
Synthesis
Totalsynthesen
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Summary:An approach to cyclic nitrones from N‐hydroxylactam derivatives is documented. The nucleophilic addition of an organolithium reagent to an N‐OSEM [SEM=2‐(trimethylsilyl)ethoxymethyl] lactam forms a five‐membered chelated intermediate, which undergoes both elimination and deprotection to give a fully substituted nitrone in a one‐pot process. When combined with the N‐oxidation of easily available chiral lactams, this method becomes especially useful for the quick synthesis of chiral nitrones in enantio‐pure form, enabling the concise total synthesis of cylindricine C. Vollständig substituierte cyclische Nitrone wurden aus N‐Hydroxylactamen hergestellt. Die Reaktion verläuft in einem Eintopfprozess über die nukleophile Addition eines Organolithium‐Reagens und anschließende Eliminierung. In Kombination mit der N‐Oxidation eines chiralen Lactams erlaubt die Methode die Verwendung eines leicht verfügbaren Lactams als chirales Nitronäquivalent und ermöglicht die enantioselektive Totalsynthese von Cylindricin C.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201901049