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    Stereoselective Additions to Cyclopropenes

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    Edwards_ku_0099D_15877_DATA_1.pdf (6.512Mb)
    Issue Date
    2018-05-31
    Author
    Edwards, Andrew
    Publisher
    University of Kansas
    Format
    360 pages
    Type
    Dissertation
    Degree Level
    Ph.D.
    Discipline
    Chemistry
    Rights
    Copyright held by the author.
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    Abstract
    This thesis concerns strain-release driven stereoselective addition reactions to cyclopropenes leading to the synthesis of medium-sized 8-membered 1,5-dioxocane ring structures, optically active cyclopropylboronates, and densely functionalized cyclopropane scaffolds via the addition of highly reactive carbon nucleophiles. This thesis is separated into three chapters detailing the background, development, optimization, scope, and limitations of each developed methodology. Chapter one describes a strain-release driven nucleophilic (4+4) cyclodimerization of cyclopropenes providing a fused three ring system possessing a medium-sized eight member ring core. The process is believed to proceed via a face-selective nucleophilic attack of an alkoxide on the strained double bond of cyclopropene followed by highly diastereoselective nucleophilic ring closure. Additionally, a newly developed expedited and cost saving method of accessing prochiral cyclopropenes possessing an unsubstituted double bond via Rh(II)-catalyzed [2+1] cycloaddition is detailed. Chapter two describes the directed rhodium(I)-catalyzed asymmetric hydroboration of cyclopropenes bearing ester and amide functions as directing groups. Hydroboration of esters provided variable results sensitive to the identity of the substituent on the opposing face of cyclopropene. The utilization of a much more Lewis basic amide function as a highly efficient directing group along with the development of a new class of prochiral cyclopropenyl amides is detailed. Chapter three describes the directed copper(I)-catalyzed ring retentive addition of Grignard reagents across the stained double bond of cyclopropenes. The high degree of conformational and configurational stability of the intermediate cyclopropyl Grignard reagent allowed for highly diastereoselective trapping with a variety of electrophiles, providing the possibility of constructing two carbon-carbon bonds and up to four contiguous stereocenters in a single chemical step.
    URI
    http://hdl.handle.net/1808/27877
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    • Chemistry Dissertations and Theses [336]
    • Dissertations [4321]

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    785-864-8983
    KU Libraries
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    785-864-8983

    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
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    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
     

     

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