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    Understanding Halide Counterion Effects in Enantioselective Ruthenium-Catalyzed Carbonyl (α-Aryl)allylation: Alkynes as Latent Allenes and Trifluoroethanol-Enhanced Turnover in The Conversion of Ethanol to Higher Alcohols via Hydrogen Auto-transfer

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    Type
    Article
    Authors
    Ortiz, Eliezer
    Shezaf, Jonathan Z.
    Chang, Yu-Hsiang
    Goncalves, Theo
    Huang, Kuo-Wei cc
    Krische, Michael J. cc
    KAUST Department
    Chemical Science Program
    Homogeneous Catalysis Laboratory (HCL)
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Date
    2021-10-04
    Online Publication Date
    2021-10-04
    Print Publication Date
    2021-10-13
    Embargo End Date
    2022-10-04
    Submitted Date
    2021-07-27
    Permanent link to this record
    http://hdl.handle.net/10754/672172
    
    Metadata
    Show full item record
    Abstract
    Crystallographic characterization of RuX(CO)(η3-C3H5)(JOSIPHOS), where X = Cl, Br, or I, reveals a halide-dependent diastereomeric preference that defines metal-centered stereogenicity and, therefrom, the enantioselectivity of C-C coupling in ruthenium-catalyzed anti-diastereo- and enantioselective C-C couplings of primary alcohols with 1-aryl-1-propynes to form products of carbonyl anti-(α-aryl)allylation. Computational studies reveal that a non-classical hydrogen bond between iodide and the aldehyde formyl CH bond stabilizes the favored transition state for carbonyl addition. An improved catalytic system enabling previously unattainable transformations was developed that employs an iodide-containing precatalyst, RuI(CO)3(η3-C3H5), in combination with trifluoroethanol, as illustrated by the first enantioselective ruthenium-catalyzed C-C couplings of ethanol to form higher alcohols.
    Citation
    Ortiz, E., Shezaf, J. Z., Chang, Y.-H., Gonçalves, T. P., Huang, K.-W., & Krische, M. J. (2021). Understanding Halide Counterion Effects in Enantioselective Ruthenium-Catalyzed Carbonyl (α-Aryl)allylation: Alkynes as Latent Allenes and Trifluoroethanol-Enhanced Turnover in The Conversion of Ethanol to Higher Alcohols via Hydrogen Auto-transfer. Journal of the American Chemical Society. doi:10.1021/jacs.1c07857
    Sponsors
    The Robert A. Welch Foundation (F-0038) and the NIH-NIGMS (RO1-GM069445) are acknowledged for partial support of this research. We are grateful for the assistance of Dr. Vincent Lynch for the acquisition and analysis of X-ray diffraction data. The service of Ibex, Shaheen 2 High Performance Computing Facilities, was provided by King Abdullah University of Science and Technology (KAUST).
    Publisher
    American Chemical Society (ACS)
    Journal
    Journal of the American Chemical Society
    DOI
    10.1021/jacs.1c07857
    PubMed ID
    34606271
    Additional Links
    https://pubs.acs.org/doi/10.1021/jacs.1c07857
    ae974a485f413a2113503eed53cd6c53
    10.1021/jacs.1c07857
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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