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    Tricyclic Sulfoxide–Alkene Hybrid Ligands for Chiral Rh(I) Complexes: The “Matched” Diastereomer Catalyzes Asymmetric C–C Bond Formations

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    Name:
    A_om-2020-00094z.R1.pdf
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    5.128Mb
    Format:
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    Description:
    Accepted manuscript
    Embargo End Date:
    2021-03-19
    Download
    Type
    Article
    Authors
    Nikol, Alexander
    Zhang, Ziyun
    Chelouan, Ahmed
    Falivene, Laura cc
    Cavallo, Luigi cc
    Herrera, Alberto
    Heinemann, Frank W. cc
    Escalona, Ana
    Frieß, Sibylle
    Grasruck, Alexander
    Dorta, Romano cc
    KAUST Department
    Chemical Science Program
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Date
    2020-03-19
    Online Publication Date
    2020-03-19
    Print Publication Date
    2020-04-27
    Embargo End Date
    2021-03-19
    Submitted Date
    2020-02-10
    Permanent link to this record
    http://hdl.handle.net/10754/662258
    
    Metadata
    Show full item record
    Abstract
    Deprotonation of phenyldibenzo[b,f]tropylidene (8) with LDA/t-BuOK followed by quenching with either diastereomer of inexpensive glucose-based t-Bu-sulfinate (R)- or (S)-11 affords a sulfoxide−alkene hybrid ligand as the diastereomeric pairs (SS,SC)-9/(SS,RC)-10 and (RS,RC)-9/ (RS,SC)-10, respectively, which via chromatographic/recrystallization may be separated into the four isomers. The optically pure diastereomeric ligands (SS,SC)-9 and (SS,RC)-10 react with [RhCl(coe)2]2 to form the dinuclear complexes (RS,SC)-11 and (RS,RC)-12, respectively, in which the bidentate ligands coordinate the metal centers through the sulfur and alkene donor functions. These complexes catalyze the conjugate addition of arylboronic acids to cyclic Michael acceptors with enantioselectivities of up to 99% ee. DFT calculations show the preponderant influence of planar chirality of the ligand alkene function. The enantioselectivity switch observed between (RS,SC)-11 and (RS,RC)-12 is explained by the inverted cis−trans coordinations of the substrate molecules in catalytic steps.
    Citation
    Nikol, A., Zhang, Z., Chelouan, A., Falivene, L., Cavallo, L., Herrera, A., … Dorta, R. (2020). Tricyclic Sulfoxide–Alkene Hybrid Ligands for Chiral Rh(I) Complexes: The “Matched” Diastereomer Catalyzes Asymmetric C–C Bond Formations. Organometallics. doi:10.1021/acs.organomet.0c00094
    Sponsors
    We thank Prof. Anthony Linden (University of Zurich) for solving the crystal structure of 8 and Ms. Christina Wronna for carrying out the elemental analyses. Financial support by Friedrich–Alexander University and King Abdullah University of Science and Technology (KAUST) is acknowledged. For computer time, this research used the resources of the Supercomputing Laboratory (KSL) at KAUST.
    Publisher
    American Chemical Society (ACS)
    Journal
    Organometallics
    DOI
    10.1021/acs.organomet.0c00094
    Additional Links
    https://pubs.acs.org/doi/10.1021/acs.organomet.0c00094
    Relations
    Is Supplemented By:
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    ae974a485f413a2113503eed53cd6c53
    10.1021/acs.organomet.0c00094
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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