Approach to Fully Substituted Cyclic Nitrones from N‐Hydroxylactam Derivatives: Development and Application to the Total Synthesis of Cylindricine C. (18th February 2019)

• Record Type: Journal Article
• Authors: Hiraoka, Shobu; Matsumoto, Tsutomu; Matsuzaka, Koki; Sato, Takaaki; Chida, Noritaka
• Is Part Of: Angewandte Chemie. Volume 131:Number 13(2019)
• Page Start: 4425
• Page End: 4429
• Publication Date: 2019-02-18
• Subjects: Amide -- Nitrone -- Nukleophile Addition -- Synthesemethoden -- Totalsynthesen; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201901049
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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.