Catalytic asymmetric Nozaki-Hiyama reactions with a tridentate bis(oxazolinyl)carbazole ligand

Masahiro Inoue, Takahiro Suzuki, Akihiro Kinoshita, Masahisa Nakada

    Research output: Contribution to journalArticle

    35 Citations (Scopus)

    Abstract

    Nozaki-Hiyama reactions are powerful CrII-mediated C - C bond-forming reactions conducted under mild conditions that show excellent compatibility with various functional groups. Therefore, Nozaki-Hiyama reactions have been utilized for many total syntheses of complex natural products, but at least two equivalents of CrII salt are required to complete the reaction because CrII salt is a one-electron donor. In 1996, however, the quantity of CrII salts required was successfully reduced by a catalytic redox system reported by Fürstner and Shi. Since the report by Fürstner, the catalytic asymmetric Nozaki-Hiyama reactions have attracted attention because they would allow control over enantioselectivity, thereby further enhancing the versatility of Nozaki-Hiyama reactions. In this review, we describe the development of a tridentate bis(oxazolinyl)carbazole ligand for the catalytic asymmetric Nozaki-Hiyama allylation, methallylation, propargylation, and allenylation. Also described are their successful applications to the highly stereoselective construction of the side chain of calcitriol lactone, as well as structure elucidation and the enantioselective first total synthesis of the potent 3-hydroxy-3-methylglutaryl coenzyme A reductase inhibitors, FR901512 and FR901516.

    Original languageEnglish
    Pages (from-to)169-181
    Number of pages13
    JournalChemical Record
    Volume8
    Issue number3
    DOIs
    Publication statusPublished - 2008

    Fingerprint

    Salts
    Ligands
    Allylation
    Coenzymes
    Calcitriol
    Enantioselectivity
    Lactones
    Biological Products
    Functional groups
    Oxidation-Reduction
    Oxidoreductases
    Electrons
    carbazole
    3-hydroxy-3-methylglutaryl-coenzyme A
    FR901512

    Keywords

    • Asymmetric catalysis
    • Ligand
    • Nozaki-Hiyama reaction

    ASJC Scopus subject areas

    • Chemistry(all)
    • Chemical Engineering(all)
    • Materials Chemistry
    • Biochemistry
    • Biochemistry, medical

    Cite this

    Catalytic asymmetric Nozaki-Hiyama reactions with a tridentate bis(oxazolinyl)carbazole ligand. / Inoue, Masahiro; Suzuki, Takahiro; Kinoshita, Akihiro; Nakada, Masahisa.

    In: Chemical Record, Vol. 8, No. 3, 2008, p. 169-181.

    Research output: Contribution to journalArticle

    Inoue, Masahiro ; Suzuki, Takahiro ; Kinoshita, Akihiro ; Nakada, Masahisa. / Catalytic asymmetric Nozaki-Hiyama reactions with a tridentate bis(oxazolinyl)carbazole ligand. In: Chemical Record. 2008 ; Vol. 8, No. 3. pp. 169-181.
    @article{b520e50d76834b778cc90b81e95ffb28,
    title = "Catalytic asymmetric Nozaki-Hiyama reactions with a tridentate bis(oxazolinyl)carbazole ligand",
    abstract = "Nozaki-Hiyama reactions are powerful CrII-mediated C - C bond-forming reactions conducted under mild conditions that show excellent compatibility with various functional groups. Therefore, Nozaki-Hiyama reactions have been utilized for many total syntheses of complex natural products, but at least two equivalents of CrII salt are required to complete the reaction because CrII salt is a one-electron donor. In 1996, however, the quantity of CrII salts required was successfully reduced by a catalytic redox system reported by F{\"u}rstner and Shi. Since the report by F{\"u}rstner, the catalytic asymmetric Nozaki-Hiyama reactions have attracted attention because they would allow control over enantioselectivity, thereby further enhancing the versatility of Nozaki-Hiyama reactions. In this review, we describe the development of a tridentate bis(oxazolinyl)carbazole ligand for the catalytic asymmetric Nozaki-Hiyama allylation, methallylation, propargylation, and allenylation. Also described are their successful applications to the highly stereoselective construction of the side chain of calcitriol lactone, as well as structure elucidation and the enantioselective first total synthesis of the potent 3-hydroxy-3-methylglutaryl coenzyme A reductase inhibitors, FR901512 and FR901516.",
    keywords = "Asymmetric catalysis, Ligand, Nozaki-Hiyama reaction",
    author = "Masahiro Inoue and Takahiro Suzuki and Akihiro Kinoshita and Masahisa Nakada",
    year = "2008",
    doi = "10.1002/tcr.20148",
    language = "English",
    volume = "8",
    pages = "169--181",
    journal = "Chemical record (New York, N.Y.)",
    issn = "1527-8999",
    publisher = "John Wiley and Sons Inc.",
    number = "3",

    }

    TY - JOUR

    T1 - Catalytic asymmetric Nozaki-Hiyama reactions with a tridentate bis(oxazolinyl)carbazole ligand

    AU - Inoue, Masahiro

    AU - Suzuki, Takahiro

    AU - Kinoshita, Akihiro

    AU - Nakada, Masahisa

    PY - 2008

    Y1 - 2008

    N2 - Nozaki-Hiyama reactions are powerful CrII-mediated C - C bond-forming reactions conducted under mild conditions that show excellent compatibility with various functional groups. Therefore, Nozaki-Hiyama reactions have been utilized for many total syntheses of complex natural products, but at least two equivalents of CrII salt are required to complete the reaction because CrII salt is a one-electron donor. In 1996, however, the quantity of CrII salts required was successfully reduced by a catalytic redox system reported by Fürstner and Shi. Since the report by Fürstner, the catalytic asymmetric Nozaki-Hiyama reactions have attracted attention because they would allow control over enantioselectivity, thereby further enhancing the versatility of Nozaki-Hiyama reactions. In this review, we describe the development of a tridentate bis(oxazolinyl)carbazole ligand for the catalytic asymmetric Nozaki-Hiyama allylation, methallylation, propargylation, and allenylation. Also described are their successful applications to the highly stereoselective construction of the side chain of calcitriol lactone, as well as structure elucidation and the enantioselective first total synthesis of the potent 3-hydroxy-3-methylglutaryl coenzyme A reductase inhibitors, FR901512 and FR901516.

    AB - Nozaki-Hiyama reactions are powerful CrII-mediated C - C bond-forming reactions conducted under mild conditions that show excellent compatibility with various functional groups. Therefore, Nozaki-Hiyama reactions have been utilized for many total syntheses of complex natural products, but at least two equivalents of CrII salt are required to complete the reaction because CrII salt is a one-electron donor. In 1996, however, the quantity of CrII salts required was successfully reduced by a catalytic redox system reported by Fürstner and Shi. Since the report by Fürstner, the catalytic asymmetric Nozaki-Hiyama reactions have attracted attention because they would allow control over enantioselectivity, thereby further enhancing the versatility of Nozaki-Hiyama reactions. In this review, we describe the development of a tridentate bis(oxazolinyl)carbazole ligand for the catalytic asymmetric Nozaki-Hiyama allylation, methallylation, propargylation, and allenylation. Also described are their successful applications to the highly stereoselective construction of the side chain of calcitriol lactone, as well as structure elucidation and the enantioselective first total synthesis of the potent 3-hydroxy-3-methylglutaryl coenzyme A reductase inhibitors, FR901512 and FR901516.

    KW - Asymmetric catalysis

    KW - Ligand

    KW - Nozaki-Hiyama reaction

    UR - http://www.scopus.com/inward/record.url?scp=53249107785&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=53249107785&partnerID=8YFLogxK

    U2 - 10.1002/tcr.20148

    DO - 10.1002/tcr.20148

    M3 - Article

    C2 - 18563811

    AN - SCOPUS:53249107785

    VL - 8

    SP - 169

    EP - 181

    JO - Chemical record (New York, N.Y.)

    JF - Chemical record (New York, N.Y.)

    SN - 1527-8999

    IS - 3

    ER -