KUKU

KU ScholarWorks

  • myKU
  • Email
  • Enroll & Pay
  • KU Directory
    • Login
    View Item 
    •   KU ScholarWorks
    • Dissertations and Theses
    • Dissertations
    • View Item
    •   KU ScholarWorks
    • Dissertations and Theses
    • Dissertations
    • View Item
    JavaScript is disabled for your browser. Some features of this site may not work without it.

    Development of Methods for the Heteroatom Functionalization of Cyclopropenes

    Thumbnail
    View/Open
    Alnasleh_ku_0099D_11697_DATA_1.pdf (3.844Mb)
    Issue Date
    2011-08-31
    Author
    Alnasleh, Bassam Kamal
    Publisher
    University of Kansas
    Format
    303 pages
    Type
    Dissertation
    Degree Level
    Ph.D.
    Discipline
    Chemistry
    Rights
    This item is protected by copyright and unless otherwise specified the copyright of this thesis/dissertation is held by the author.
    Metadata
    Show full item record
    Abstract
    The main focus of this thesis is the stereoselective funtionalization of cyclopropenes mainly via the addition of H-X (hetroatom-hydrogen) moieties across the strained double bond. It is broken up into three chapters, each one devoted to different methods allowing for direct funtionalization of these uniquely interesting and highly reactive carbocycles. The first chapter is devoted to the palladium catalyzed hydrophosphorylation and hydrophosphinylation of cyclopropenes. This methodology allows for the direct ring retentive funtionalization of cyclopropenes with a pronucleophilic entity, which up until now has been extremely scarce. Aside from the synthetic value, the methodology also provides access to highly funtionalized stereodefined cyclopropylphosphonates which have a proven track record as medicinaly relevant substrates. The second chapter focuses on intermolecular formal nucleophilic substitutions of bromocyclopropanes. This method aims for the construction of highly functionalized cyclopropyl ethers via direct nucleophilic attack of O-based pronucleophiles to in situ generated, highly reactive cyclopropene intermediates. The diastereoselectivity of the reaction is controlled either by sterics or through directing effects providing highly streo-defined donor-acceptor cyclopropanes. Chapter three describes highly efficient and diastereoselective medium ring closures occurring upon intramolecular attack of a tethered alkoxide nucleophile at bromocyclopropane. The reaction proceeds via initial 1,2-dehydrobromination to produce a cyclopropene intermediate, followed by nucleophilic addition across the strained C=C bond, to produce cyclopropane-fused medium heterocycles.
    URI
    http://hdl.handle.net/1808/10704
    Collections
    • Dissertations [3958]
    • Chemistry Dissertations and Theses [171]

    Items in KU ScholarWorks are protected by copyright, with all rights reserved, unless otherwise indicated.


    We want to hear from you! Please share your stories about how Open Access to this item benefits YOU.


    Contact KU ScholarWorks
    785-864-8983
    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    785-864-8983

    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    Image Credits
     

     

    Browse

    All of KU ScholarWorksCommunities & CollectionsThis Collection

    My Account

    LoginRegister

    Statistics

    View Usage Statistics

    Contact KU ScholarWorks
    785-864-8983
    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    785-864-8983

    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    Image Credits
     

     

    The University of Kansas
      Contact KU ScholarWorks
    Lawrence, KS | Maps
     
    • Academics
    • Admission
    • Alumni
    • Athletics
    • Campuses
    • Giving
    • Jobs

    The University of Kansas prohibits discrimination on the basis of race, color, ethnicity, religion, sex, national origin, age, ancestry, disability, status as a veteran, sexual orientation, marital status, parental status, gender identity, gender expression and genetic information in the University’s programs and activities. The following person has been designated to handle inquiries regarding the non-discrimination policies: Director of the Office of Institutional Opportunity and Access, IOA@ku.edu, 1246 W. Campus Road, Room 153A, Lawrence, KS, 66045, (785)864-6414, 711 TTY.

     Contact KU
    Lawrence, KS | Maps