Development of Transition-Metal Catalyzed Carbon-Carbon Bond Forming Reactions Public Deposited

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  • March 19, 2019
  • Lainhart, Brendan
    • Affiliation: College of Arts and Sciences, Department of Chemistry
  • Chapter One discusses our efforts towards a Rhodium-catalyzed [4 + 2 + 2] cycloaddition of diene-allenes with exogenous allenes. Our efforts began with the development of a racemic reaction achieving high yields through the use of Rh-phosphoramidite and Rh-phosphite catalyst systems. Further, we discuss the challenging development of an enantioselective variant and the methods we used to avoid the problematic [4 + 2] side reaction. We demonstrate that in these reactions, a Rh-H8-monophos complex can produce highly enantioenriched cyclooctanoid products in decent yield. The chapter finishes with a discussion of the potential reaction mechanisms and the evidence thereof. Chapter Two describes the initial efforts towards three Pd-catalyzed C-C bond forming reactions of alkyl halides: 1) The improvement of the alkyl-Heck type cyclization of alkyl iodides; 2) The development of the alkyl-Heck type cyclization of primary alkyl bromides; 3) Efforts towards the enantioselective carbonylation of alkyl iodides using both steric selectivity and directing group based selectivity.
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  • In Copyright
  • Dempsey, Jillian
  • Lockett, Matthew
  • Alexanian, Erik
  • Meek, Simon
  • Johnson, Jeffrey
  • Doctor of Philosophy
Degree granting institution
  • University of North Carolina at Chapel Hill Graduate School
Graduation year
  • 2015
Place of publication
  • Chapel Hill, NC
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