Asymmetric Total Synthesis of (−)‐Stemonamine and Its Stereochemical Stability. Issue 7 (16th January 2018)

• Record Type: Journal Article
• Authors: Fujita, Satoshi; Nishikawa, Keisuke; Iwata, Takayuki; Tomiyama, Taishi; Ikenaga, Hiroshi; Matsumoto, Kenji; Shindo, Mitsuru
• Is Part Of: Chemistry. Volume 24:Issue 7(2018)
• Page Start: 1539
• Page End: 1543
• Publication Date: 2018-01-16
• Subjects: alkaloids -- asymmetric synthesis -- Dieckmann condensation -- total synthesis -- ynolate -- pyrrolo[1, 2-a]azepine core; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201706057
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The first asymmetric total synthesis of (−)‐stemonamine is described. The key reactions included intramolecular acylation to construct the seven‐membered ring and a tandem [2+2] cycloaddition‐Dieckmann condensation reaction using an ynolate to form the fully substituted cyclopentenone moiety. Racemization and epimerization of the natural product were first experimentally demonstrated. Abstract : A pioneering synthesis : The first total synthesis of nonracemic (−)‐stemonamine is achieved in 17 steps from known compounds. Key reactions include intramolecular acylation and ynolate‐initiated tandem [2+2] cycloaddition‐Dieckmann condensation.