Synthesis of optically active (+)-19-nortestosterone by asymmetric bis-annulation reaction

Isao Shimizu, Yoichiro Naito, Jiro Tsuji

    Research output: Contribution to journalArticle

    35 Citations (Scopus)

    Abstract

    Michael reaction of 1,7-pctadien-3-one with 2-methylcyclopentane-1,3-dione, followed by intramolecular aldol condensation promoted by L-amino acids produced the optically active (+)-4-(3-butenyl)-7a-methyl-5,6,7,7a-tetrahydroindane-1,5-dione in high chemical and optical yields. The PdCl2-catalyzed oxidation of the terminal double bond gave the methyl ketone, which had 76% optical purity and was made 100% optically pure by recrystallization. Then aldol condensation afforded the tricyclic ketone, which was alkylated with 3-butenyl iodide to afford (-)-3β-t-butoxy-2,3,3a,4,5,7,8,9,9aβ,9bα-decahydro-6-(3-butenyl)-3aβ-methyl-1H-benz[e]inden-7-one. The synthesis of this compound means the total synthesis of (+)-19-nortestosterone.

    Original languageEnglish
    Pages (from-to)487-490
    Number of pages4
    JournalTetrahedron Letters
    Volume21
    Issue number5
    DOIs
    Publication statusPublished - 1980

    Fingerprint

    Nandrolone
    Ketones
    Condensation
    Iodides
    Amino Acids
    Oxidation
    3-hydroxybutanal
    palladium chloride
    methylcyclopentane

    ASJC Scopus subject areas

    • Biochemistry
    • Organic Chemistry
    • Drug Discovery

    Cite this

    Synthesis of optically active (+)-19-nortestosterone by asymmetric bis-annulation reaction. / Shimizu, Isao; Naito, Yoichiro; Tsuji, Jiro.

    In: Tetrahedron Letters, Vol. 21, No. 5, 1980, p. 487-490.

    Research output: Contribution to journalArticle

    Shimizu, Isao ; Naito, Yoichiro ; Tsuji, Jiro. / Synthesis of optically active (+)-19-nortestosterone by asymmetric bis-annulation reaction. In: Tetrahedron Letters. 1980 ; Vol. 21, No. 5. pp. 487-490.
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    abstract = "Michael reaction of 1,7-pctadien-3-one with 2-methylcyclopentane-1,3-dione, followed by intramolecular aldol condensation promoted by L-amino acids produced the optically active (+)-4-(3-butenyl)-7a-methyl-5,6,7,7a-tetrahydroindane-1,5-dione in high chemical and optical yields. The PdCl2-catalyzed oxidation of the terminal double bond gave the methyl ketone, which had 76{\%} optical purity and was made 100{\%} optically pure by recrystallization. Then aldol condensation afforded the tricyclic ketone, which was alkylated with 3-butenyl iodide to afford (-)-3β-t-butoxy-2,3,3a,4,5,7,8,9,9aβ,9bα-decahydro-6-(3-butenyl)-3aβ-methyl-1H-benz[e]inden-7-one. The synthesis of this compound means the total synthesis of (+)-19-nortestosterone.",
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    N2 - Michael reaction of 1,7-pctadien-3-one with 2-methylcyclopentane-1,3-dione, followed by intramolecular aldol condensation promoted by L-amino acids produced the optically active (+)-4-(3-butenyl)-7a-methyl-5,6,7,7a-tetrahydroindane-1,5-dione in high chemical and optical yields. The PdCl2-catalyzed oxidation of the terminal double bond gave the methyl ketone, which had 76% optical purity and was made 100% optically pure by recrystallization. Then aldol condensation afforded the tricyclic ketone, which was alkylated with 3-butenyl iodide to afford (-)-3β-t-butoxy-2,3,3a,4,5,7,8,9,9aβ,9bα-decahydro-6-(3-butenyl)-3aβ-methyl-1H-benz[e]inden-7-one. The synthesis of this compound means the total synthesis of (+)-19-nortestosterone.

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