Discovery and development of asymmetric auto catalysis

Kenso Soai, Takanori Shibata, Itaru Sato

    Research output: Contribution to journalArticle

    81 Citations (Scopus)

    Abstract

    Asymmetric autocatalysis occurs when a chiral product operates as an asymmetric catalyst for its own production. We have discovered an asymmetric autocatalytic reaction in the enantioselective addition of dialkylzinc to pyridine-3-carbaldehyde, where the product, 3-pyridyl alkanol, acts as an asymmetric autocatalyst. A diol, ferrocenyl alkanol, 5-pyrimidyl alkanol, and 3-quinolyl alkanol were also found to be asymmetric autocatalysts for the enantioselective isopropylation of the corresponding aldehydes. Of these compounds, 5-(2-alkynyl)pyrimidyl alkanol was the best asymmetric autocatalyst, and the asymmetric autocatalytic isopropylation of the corresponding pyrimidine-5-carbaldehyde proceeded quantitatively (>99%), affording itself as a near enantiomerically pure (>99.5% ee) chiral product. When an asymmetric autocatalyst with an extremely low ee was used, the asymmetric autocatalytic reaction proceeded along with amplification of the ee, and a highly enantiomerically enriched product was obtained. When the enantioselective isopropylation of pyrimidine-5-carbaldehydes was examined in the presence of chiral organic compounds with a very low ee acting as chiral initiators, then highly enantiomerically enriched 5-pyrimidyl alkanols were obtained. Their absolute configurations were dependent upon the slight excess of enantiomer in the chiral initiators. Chiral inorganic crystals, such as quartz and sodium chlorate, also act as chiral initiators. In conjunction with asymmetric autocatalysis, the chirality of organic compounds with a high enantiomeric excess has been correlated for the first time with the circularly polarized light and chiral inorganic crystals. Moreover, when an enantioselective isopropylation was examined in the absence of a chiral initiator, asymmetric induction above the detection level was observed in the product, with the ratio of the resulting predominant S- and R-isomers being almost equal. This result fulfills one of the conditions necessary for spontaneous absolute asymmetric synthesis.

    Original languageEnglish
    Pages (from-to)1063-1073
    Number of pages11
    JournalBulletin of the Chemical Society of Japan
    Volume77
    Issue number6
    DOIs
    Publication statusPublished - 2004

    Fingerprint

    Organic compounds
    Catalysis
    Crystals
    Quartz
    Enantiomers
    Chirality
    Light polarization
    Aldehydes
    Isomers
    Amplification
    Catalysts
    pyrimidine
    pyridine
    sodium chlorate

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Discovery and development of asymmetric auto catalysis. / Soai, Kenso; Shibata, Takanori; Sato, Itaru.

    In: Bulletin of the Chemical Society of Japan, Vol. 77, No. 6, 2004, p. 1063-1073.

    Research output: Contribution to journalArticle

    @article{30a4f63b5f6a4f08b6f9d83f7236aca9,
    title = "Discovery and development of asymmetric auto catalysis",
    abstract = "Asymmetric autocatalysis occurs when a chiral product operates as an asymmetric catalyst for its own production. We have discovered an asymmetric autocatalytic reaction in the enantioselective addition of dialkylzinc to pyridine-3-carbaldehyde, where the product, 3-pyridyl alkanol, acts as an asymmetric autocatalyst. A diol, ferrocenyl alkanol, 5-pyrimidyl alkanol, and 3-quinolyl alkanol were also found to be asymmetric autocatalysts for the enantioselective isopropylation of the corresponding aldehydes. Of these compounds, 5-(2-alkynyl)pyrimidyl alkanol was the best asymmetric autocatalyst, and the asymmetric autocatalytic isopropylation of the corresponding pyrimidine-5-carbaldehyde proceeded quantitatively (>99{\%}), affording itself as a near enantiomerically pure (>99.5{\%} ee) chiral product. When an asymmetric autocatalyst with an extremely low ee was used, the asymmetric autocatalytic reaction proceeded along with amplification of the ee, and a highly enantiomerically enriched product was obtained. When the enantioselective isopropylation of pyrimidine-5-carbaldehydes was examined in the presence of chiral organic compounds with a very low ee acting as chiral initiators, then highly enantiomerically enriched 5-pyrimidyl alkanols were obtained. Their absolute configurations were dependent upon the slight excess of enantiomer in the chiral initiators. Chiral inorganic crystals, such as quartz and sodium chlorate, also act as chiral initiators. In conjunction with asymmetric autocatalysis, the chirality of organic compounds with a high enantiomeric excess has been correlated for the first time with the circularly polarized light and chiral inorganic crystals. Moreover, when an enantioselective isopropylation was examined in the absence of a chiral initiator, asymmetric induction above the detection level was observed in the product, with the ratio of the resulting predominant S- and R-isomers being almost equal. This result fulfills one of the conditions necessary for spontaneous absolute asymmetric synthesis.",
    author = "Kenso Soai and Takanori Shibata and Itaru Sato",
    year = "2004",
    doi = "10.1246/bcsj.77.1063",
    language = "English",
    volume = "77",
    pages = "1063--1073",
    journal = "Bulletin of the Chemical Society of Japan",
    issn = "0009-2673",
    publisher = "Chemical Society of Japan",
    number = "6",

    }

    TY - JOUR

    T1 - Discovery and development of asymmetric auto catalysis

    AU - Soai, Kenso

    AU - Shibata, Takanori

    AU - Sato, Itaru

    PY - 2004

    Y1 - 2004

    N2 - Asymmetric autocatalysis occurs when a chiral product operates as an asymmetric catalyst for its own production. We have discovered an asymmetric autocatalytic reaction in the enantioselective addition of dialkylzinc to pyridine-3-carbaldehyde, where the product, 3-pyridyl alkanol, acts as an asymmetric autocatalyst. A diol, ferrocenyl alkanol, 5-pyrimidyl alkanol, and 3-quinolyl alkanol were also found to be asymmetric autocatalysts for the enantioselective isopropylation of the corresponding aldehydes. Of these compounds, 5-(2-alkynyl)pyrimidyl alkanol was the best asymmetric autocatalyst, and the asymmetric autocatalytic isopropylation of the corresponding pyrimidine-5-carbaldehyde proceeded quantitatively (>99%), affording itself as a near enantiomerically pure (>99.5% ee) chiral product. When an asymmetric autocatalyst with an extremely low ee was used, the asymmetric autocatalytic reaction proceeded along with amplification of the ee, and a highly enantiomerically enriched product was obtained. When the enantioselective isopropylation of pyrimidine-5-carbaldehydes was examined in the presence of chiral organic compounds with a very low ee acting as chiral initiators, then highly enantiomerically enriched 5-pyrimidyl alkanols were obtained. Their absolute configurations were dependent upon the slight excess of enantiomer in the chiral initiators. Chiral inorganic crystals, such as quartz and sodium chlorate, also act as chiral initiators. In conjunction with asymmetric autocatalysis, the chirality of organic compounds with a high enantiomeric excess has been correlated for the first time with the circularly polarized light and chiral inorganic crystals. Moreover, when an enantioselective isopropylation was examined in the absence of a chiral initiator, asymmetric induction above the detection level was observed in the product, with the ratio of the resulting predominant S- and R-isomers being almost equal. This result fulfills one of the conditions necessary for spontaneous absolute asymmetric synthesis.

    AB - Asymmetric autocatalysis occurs when a chiral product operates as an asymmetric catalyst for its own production. We have discovered an asymmetric autocatalytic reaction in the enantioselective addition of dialkylzinc to pyridine-3-carbaldehyde, where the product, 3-pyridyl alkanol, acts as an asymmetric autocatalyst. A diol, ferrocenyl alkanol, 5-pyrimidyl alkanol, and 3-quinolyl alkanol were also found to be asymmetric autocatalysts for the enantioselective isopropylation of the corresponding aldehydes. Of these compounds, 5-(2-alkynyl)pyrimidyl alkanol was the best asymmetric autocatalyst, and the asymmetric autocatalytic isopropylation of the corresponding pyrimidine-5-carbaldehyde proceeded quantitatively (>99%), affording itself as a near enantiomerically pure (>99.5% ee) chiral product. When an asymmetric autocatalyst with an extremely low ee was used, the asymmetric autocatalytic reaction proceeded along with amplification of the ee, and a highly enantiomerically enriched product was obtained. When the enantioselective isopropylation of pyrimidine-5-carbaldehydes was examined in the presence of chiral organic compounds with a very low ee acting as chiral initiators, then highly enantiomerically enriched 5-pyrimidyl alkanols were obtained. Their absolute configurations were dependent upon the slight excess of enantiomer in the chiral initiators. Chiral inorganic crystals, such as quartz and sodium chlorate, also act as chiral initiators. In conjunction with asymmetric autocatalysis, the chirality of organic compounds with a high enantiomeric excess has been correlated for the first time with the circularly polarized light and chiral inorganic crystals. Moreover, when an enantioselective isopropylation was examined in the absence of a chiral initiator, asymmetric induction above the detection level was observed in the product, with the ratio of the resulting predominant S- and R-isomers being almost equal. This result fulfills one of the conditions necessary for spontaneous absolute asymmetric synthesis.

    UR - http://www.scopus.com/inward/record.url?scp=3042676595&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=3042676595&partnerID=8YFLogxK

    U2 - 10.1246/bcsj.77.1063

    DO - 10.1246/bcsj.77.1063

    M3 - Article

    AN - SCOPUS:3042676595

    VL - 77

    SP - 1063

    EP - 1073

    JO - Bulletin of the Chemical Society of Japan

    JF - Bulletin of the Chemical Society of Japan

    SN - 0009-2673

    IS - 6

    ER -