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Preparation and Synthetic Applications of Chiral Alkyl Boronates and Unsaturated Alkenyl Boronates

  • Author / Creator
    Lee, Jack C. H.
  • As Organic Chemistry evolves into the 21st Century, the goal of this discipline has altered dramatically from merely accessing target molecules to efficiently synthesizing these compounds with minimization of non-strategic functional group manipulations and interconversions. Organoboron reagents represent one of the potential solutions towards reaching this goal. These versatile compounds can either be used to construct the desired carbon−carbon bond through various cross-coupling reactions, or be converted directly to the desired functionality through different chemical reactions. Direct transformations make interconversions between different functional groups unnecessary, thus making the overall process step-economical. In this thesis, several synthetic methods were developed to synthesize chiral alkyl boronates or alkenyl boronates through metal-catalyzed chemical transformations. These methodologies are based on early introduction strategy which applies well-established synthetic protocols to substrates with a pre-installed boronyl moiety. The subsequent applications of these compounds were also investigated, leading to a variety of synthetically valuable adducts. In order to access novel chiral secondary alkyl boronates, catalytic asymmetric conjugate addition reactions of 3-boronyl -unsaturated esters with Grignard reagents were developed. Chapter 2 describes the details of optimization of this methodology and the applications of the chiral alkyl boronate products. Aiming to explore the intrinsic reactivity of enantioenriched 1,1-diboron compounds, their synthesis was accomplished for the first time by performing asymmetric conjugate borylation on 3-boronyl enoates. The resulting optically enriched 1,1-diboron compounds were found to be excellent cross-coupling partners in Suzuki-Miyaura cross-couplings, leading to chiral alkyl boronates with excellent enantioselectivity. The details of these studies are presented in Chapter 3. In order to conduct a thorough examination of substrate scope in asymmetric conjugate reductions of 3-boronyl-3-aryl -unsaturated esters, a diastereoselective protocol for the preparation of these alkenyl boronates through Heck coupling was developed. In Chapter 4, the optimization of the coupling process, the substrate scope, and the subsequent application of these alkenyl boronates are discussed. Due to the synthetic potential of cyclic alkenyl boronates, new methods for their efficient synthesis are desirable. In Chapter 5, the preparation of novel cyclic alkenyl boronates through gold-catalyzed enyne cycloisomerizations is presented.

  • Subjects / Keywords
  • Graduation date
    2013-06
  • Type of Item
    Thesis
  • Degree
    Doctor of Philosophy
  • DOI
    https://doi.org/10.7939/R36K8M
  • License
    This thesis is made available by the University of Alberta Libraries with permission of the copyright owner solely for non-commercial purposes. This thesis, or any portion thereof, may not otherwise be copied or reproduced without the written consent of the copyright owner, except to the extent permitted by Canadian copyright law.
  • Language
    English
  • Institution
    University of Alberta
  • Degree level
    Doctoral
  • Department
    • Department of Chemistry
  • Supervisor / co-supervisor and their department(s)
    • Hall, Dennis G. (Department of Chemistry, University of Alberta)
  • Examining committee members and their departments
    • Bergens, Steven H. (Department of Chemistry, University of Alberta)
    • Organ, Michael G. (Department of Chemistry, York University)
    • Harynuk, James (Department of Chemistry, University of Alberta)
    • Stryker, Jeffrey M. (Department of Chemistry, University of Alberta)
    • West, Frederick G. (Department of Chemistry, University of Alberta)