Georgetown University LogoGeorgetown University Library LogoDigitalGeorgetown Home
    • Login
    View Item 
    •   DigitalGeorgetown Home
    • Georgetown University Institutional Repository
    • Georgetown College
    • Department of Chemistry
    • Graduate Theses and Dissertations - Chemistry
    • View Item
    •   DigitalGeorgetown Home
    • Georgetown University Institutional Repository
    • Georgetown College
    • Department of Chemistry
    • Graduate Theses and Dissertations - Chemistry
    • View Item
    JavaScript is disabled for your browser. Some features of this site may not work without it.

    Lewis acid assisted metal-ligand bifunctional hydrogenation of amides

    Cover for Lewis acid assisted metal-ligand bifunctional hydrogenation of amides
    View/Open
    View/Open: synnottStephanee.pdf (699kB) Bookview

    Creator
    Synnott, Stephanee Lynn.
    Description
    Thesis (M.S.)--Georgetown University, 2009.; Includes bibliographical references. In the past decade, metal-ligand bifuctional catalysis has been a growing interest in the field of hydration of polar double bonds. In particular, these catalysts have provided a new mechanistic approach for the direct reduction of carbonyl compounds.1 The most well studied example of the metal-ligand bifuctional catalysis is Noyori's Ru catalyst shown in figure 1. The hydrogens for the reduction are located on the ruthenium metal and the amine ligand. The hydridic Ru-H and the protic N-H are simultaneously inserted to the carbonyl, which has a partial negative charge on the oxygen and a partial positive charge on the carbon, to form a six member transition state, resulting in an S alcohol.6 This type of catalysis however, has not been effective for amide reductions.; Because of the growing interest in developing mild and catalytic methods for reduction of amides, we propose a modification to the typical Noyori system which is designed to expand metal-ligand bifuctional activity to amide hydrogenations. Amides have a substantial contribution from a polar resonance form where a partial double bond between the carbon of the carbonyl and the nitrogen reduces the carbonyl-like character of this group and prevents normal hydrogenation.5 It is therefore proposed that a tethered Lewis acid, such as a borane, will interact with the amide nitrogen and minimize the polar resonance contribution to the carbonyl double bond. In this manner the amide will have greater "carbonyl" characteristics, and the reduction could proceed via a concerted transition state resembling the Noyori hydrogenation of ketones. Presented will be the synthesis and future goals of amide reduction activity of catalysts that contain a tethered borabicyclo[3.3.1]nonane fragment.
    Permanent Link
    http://hdl.handle.net/10822/552890
    Date Published
    2009
    Subject
    Chemistry, Inorganic
    Type
    thesis
    Publisher
    Georgetown University
    Collections
    • Graduate Theses and Dissertations - Chemistry
    Metadata
    Show full item record

    Related items

    Showing items related by title, author, creator and subject.

    • Cover for Heterogenization of Metallocyclopentadienyl Precatalysts Through Ligand Functionalization for Incorporation into Metal-Organometallic Frameworks

      Heterogenization of Metallocyclopentadienyl Precatalysts Through Ligand Functionalization for Incorporation into Metal-Organometallic Frameworks 

      Ley, Amanda Noelle (Georgetown University, 2019)
      Heterogenization of metallocyclopentadienyl ([CpxMII]+, M = Ru, Fe) precatalysts is explored through introduction to Metal-Organic Frameworks (MOFs) using [CpxMII]+-functionalized organic ligands. Such precatalytic moieties ...
    Related Items in Google Scholar

    Georgetown University Seal
    ©2009 - 2022 Georgetown University Library
    37th & O Streets NW
    Washington DC 20057-1174
    202.687.7385
    digitalscholarship@georgetown.edu
    Accessibility
     

     

    Browse

    All of DigitalGeorgetownCommunities & CollectionsCreatorsTitlesBy Creation DateThis CollectionCreatorsTitlesBy Creation Date

    My Account

    Login

    Statistics

    View Usage Statistics

    Georgetown University Seal
    ©2009 - 2022 Georgetown University Library
    37th & O Streets NW
    Washington DC 20057-1174
    202.687.7385
    digitalscholarship@georgetown.edu
    Accessibility