• Login
    View Item 
    •   SMARTech Home
    • Georgia Tech Theses and Dissertations
    • Georgia Tech Theses and Dissertations
    • View Item
    •   SMARTech Home
    • Georgia Tech Theses and Dissertations
    • Georgia Tech Theses and Dissertations
    • View Item
    JavaScript is disabled for your browser. Some features of this site may not work without it.

    Symmetry-adapted perturbation theory for organocatalysis

    Thumbnail
    View/Open
    BAKR-DISSERTATION-2018.pdf (5.074Mb)
    Date
    2018-05-03
    Author
    Bakr, Brandon Wallace
    Metadata
    Show full item record
    Abstract
    Functional-group and atomic partitions of symmetry-adapted perturbation theory (SAPT) were used, for the first time, to analyze non-covalent interactions thought to influence the selectivity of the Houk-List mechanism for intermolecular Aldol additions and organoboron catalyzed allyl additions to fluoroketones. For the Houk-List mechanism, functional-group partition of symmetry-adapted perturbation theory (F-SAPT) analysis of non-covalent interactions in the transition states that were thought to engender stereoselectivity were not found to be preferentially stabilizing for the transition states leading to the preferred products. This finding runs counter to the prevailing hypothesis that a NCHδ+···δ-O=C contact determines the stereochemical outcome. For the allyl addition to fluoroketones, F-SAPT and the atomic partition of symmetry-adapted perturbation theory (ASAPT) analyses were used to probe the non-covalent contacts that were thought to result in enantioselectivity. ASAPT confirmed all atom-atom interactions that were implicated in the literature as stabilizing or destabilizing, primarily a stabilizing F···H interaction between a fluorine of the fluoroketone and the ammonium proton of the organoboron catalyst. In addition to these studies, tools for performing F-SAPT analyses are presented, and the possibility of using local correlation approximations in double hybrid density functional theory is introduced. Finally, future studies for SAPT analysis of organocatalysis are discussed.
    URI
    http://hdl.handle.net/1853/60207
    Collections
    • Georgia Tech Theses and Dissertations [23877]
    • School of Chemistry and Biochemistry Theses and Dissertations [1525]

    Browse

    All of SMARTechCommunities & CollectionsDatesAuthorsTitlesSubjectsTypesThis CollectionDatesAuthorsTitlesSubjectsTypes

    My SMARTech

    Login

    Statistics

    View Usage StatisticsView Google Analytics Statistics
    facebook instagram twitter youtube
    • My Account
    • Contact us
    • Directory
    • Campus Map
    • Support/Give
    • Library Accessibility
      • About SMARTech
      • SMARTech Terms of Use
    Georgia Tech Library266 4th Street NW, Atlanta, GA 30332
    404.894.4500
    • Emergency Information
    • Legal and Privacy Information
    • Human Trafficking Notice
    • Accessibility
    • Accountability
    • Accreditation
    • Employment
    © 2020 Georgia Institute of Technology