Total Synthesis of (−)-Histrionicotoxin through a Stereoselective Radical Translocation–Cyclization Reaction

Manabu Sato, Hiroki Azuma, Akihiro Daigaku, Sota Sato, Kiyosei Takasu, Kentaro Okano, Hidetoshi Tokuyama

    Research output: Contribution to journalArticlepeer-review

    36 Citations (Scopus)

    Abstract

    Stereoselective total syntheses of (−)-histrionicotoxin and (−)-histrionicotoxin 235A are described. The 1-azaspiro[5.5]undecane skeleton was constructed diastereoselectively by a radical translocation–cyclization reaction involving a chiral cyclic acetal; the use of tris(trimethylsilyl)silane was crucial for the high diastereoselectivity. The cyclization product was converted into (−)-histrionicotoxin 235A through a one-pot partial-reduction–allylation reaction of a derivative containing an unprotected lactam. Finally, two terminal alkenes were transformed into enynes with the 1,3-amino alcohol protected as an oxathiazolidine oxide to complete the total synthesis of (−)-histrionicotoxin.

    Original languageEnglish
    Pages (from-to)1087-1091
    Number of pages5
    JournalAngewandte Chemie - International Edition
    Volume56
    Issue number4
    DOIs
    Publication statusPublished - 2017 Jan 19

    Keywords

    • alkaloids
    • diastereoselectivity
    • radical cyclization
    • spiro compounds
    • total synthesis

    ASJC Scopus subject areas

    • Catalysis
    • Chemistry(all)

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