Design and Synthesis of Novel Chiral Dirhodium(II) Carboxylate Complexes for Asymmetric Cyclopropanation Reactions

Frady G. Adly, Michael Gardiner, Ashraf Ghanem

    Research output: Contribution to journalArticle

    35 Citations (Scopus)

    Abstract

    A novel approach to the design of dirhodium(II) tetracarboxylates derived from (S)-amino acid ligands is reported. The approach is founded on tailoring the steric influences of the overall catalyst structure by reducing the local symmetry of the ligand's N-heterocyclic tether. The application of the new approach has led to the uncovering of [Rh2(S-tertPTTL)4] as a new member of the dirhodium(II) family with extraordinary selectivity in cyclopropanation reactions. The stereoselectivity of [Rh2(S-tertPTTL)4] was found to be comparable to that of [Rh2(S-PTAD)4] (up to >99 % ee), with the extra benefit of being more synthetically accessible. Correlations based on X-ray structures to justify the observed enantioinduction are also discussed.
    Original languageEnglish
    Pages (from-to)3447-3461
    Number of pages15
    JournalChemistry - A European Journal
    Volume22
    Issue number10
    DOIs
    Publication statusPublished - 2016

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    Ligands
    Stereoselectivity
    Amino Acids
    X rays
    Catalysts
    4-(phenylthio)-4-androstene-3,17,dione

    Cite this

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    title = "Design and Synthesis of Novel Chiral Dirhodium(II) Carboxylate Complexes for Asymmetric Cyclopropanation Reactions",
    abstract = "A novel approach to the design of dirhodium(II) tetracarboxylates derived from (S)-amino acid ligands is reported. The approach is founded on tailoring the steric influences of the overall catalyst structure by reducing the local symmetry of the ligand's N-heterocyclic tether. The application of the new approach has led to the uncovering of [Rh2(S-tertPTTL)4] as a new member of the dirhodium(II) family with extraordinary selectivity in cyclopropanation reactions. The stereoselectivity of [Rh2(S-tertPTTL)4] was found to be comparable to that of [Rh2(S-PTAD)4] (up to >99 {\%} ee), with the extra benefit of being more synthetically accessible. Correlations based on X-ray structures to justify the observed enantioinduction are also discussed.",
    keywords = "asymmetric synthesis, carbenoids, chiral catalysis, cyclopropanation, rhodium",
    author = "Adly, {Frady G.} and Michael Gardiner and Ashraf Ghanem",
    year = "2016",
    doi = "10.1002/chem.201504817",
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    pages = "3447--3461",
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    Design and Synthesis of Novel Chiral Dirhodium(II) Carboxylate Complexes for Asymmetric Cyclopropanation Reactions. / Adly, Frady G.; Gardiner, Michael; Ghanem, Ashraf.

    In: Chemistry - A European Journal, Vol. 22, No. 10, 2016, p. 3447-3461.

    Research output: Contribution to journalArticle

    TY - JOUR

    T1 - Design and Synthesis of Novel Chiral Dirhodium(II) Carboxylate Complexes for Asymmetric Cyclopropanation Reactions

    AU - Adly, Frady G.

    AU - Gardiner, Michael

    AU - Ghanem, Ashraf

    PY - 2016

    Y1 - 2016

    N2 - A novel approach to the design of dirhodium(II) tetracarboxylates derived from (S)-amino acid ligands is reported. The approach is founded on tailoring the steric influences of the overall catalyst structure by reducing the local symmetry of the ligand's N-heterocyclic tether. The application of the new approach has led to the uncovering of [Rh2(S-tertPTTL)4] as a new member of the dirhodium(II) family with extraordinary selectivity in cyclopropanation reactions. The stereoselectivity of [Rh2(S-tertPTTL)4] was found to be comparable to that of [Rh2(S-PTAD)4] (up to >99 % ee), with the extra benefit of being more synthetically accessible. Correlations based on X-ray structures to justify the observed enantioinduction are also discussed.

    AB - A novel approach to the design of dirhodium(II) tetracarboxylates derived from (S)-amino acid ligands is reported. The approach is founded on tailoring the steric influences of the overall catalyst structure by reducing the local symmetry of the ligand's N-heterocyclic tether. The application of the new approach has led to the uncovering of [Rh2(S-tertPTTL)4] as a new member of the dirhodium(II) family with extraordinary selectivity in cyclopropanation reactions. The stereoselectivity of [Rh2(S-tertPTTL)4] was found to be comparable to that of [Rh2(S-PTAD)4] (up to >99 % ee), with the extra benefit of being more synthetically accessible. Correlations based on X-ray structures to justify the observed enantioinduction are also discussed.

    KW - asymmetric synthesis

    KW - carbenoids

    KW - chiral catalysis

    KW - cyclopropanation

    KW - rhodium

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