Chiral rare earth organophosphates as homogeneous Lewis acid catalysts for the highly enantioselective hetero-Diels-Alder reactions

Hiroshi Furuno, Tetsuji Hayano, Takeshi Kambara, Yuichi Sugimoto, Takeshi Hanamoto, Yumiko Tanaka, Yong Zhi Jin, Takumi Kagawa, Junji Inanaga

    Research output: Contribution to journalArticlepeer-review

    57 Citations (Scopus)

    Abstract

    Various trivalent rare earth-chiral phosphate complexes [(R)-1-RE, (R)-3-RE, and (R)-4-Ce] were prepared and evaluated as a Lewis acid catalyst for the asymmetric hetero-Diels-Alder reaction of aldehydes with the Danishefsky's diene. Some of them effectively promoted the reaction at room temperature in the presence or absence of achiral additives under homogeneous conditions to afford the corresponding cycloadducts with high ee's (up to 99% ee). During these reactions, remarkably high asymmetric amplifications (positive nonlinear effects) were observed as the first example in the metal ion-chiral ligand 1:3 catalytic system. A scandium catalyst bearing the H 8-BNP ligand, (R)-3-Sc, could be recovered after the reaction and successfully reused for the next round of reactions. In addition, the hetero-Diels-Alder reaction of α-keto esters was effectively catalyzed by the ytterbium complex, (R)-1-Yb, without any additives thus producing the asymmetric quaternary carbon in excellent enantioselectivities (up to >99% ee).

    Original languageEnglish
    Pages (from-to)10509-10523
    Number of pages15
    JournalTetrahedron
    Volume59
    Issue number52
    DOIs
    Publication statusPublished - Dec 22 2003

    All Science Journal Classification (ASJC) codes

    • Biochemistry
    • Drug Discovery
    • Organic Chemistry

    Fingerprint

    Dive into the research topics of 'Chiral rare earth organophosphates as homogeneous Lewis acid catalysts for the highly enantioselective hetero-Diels-Alder reactions'. Together they form a unique fingerprint.

    Cite this