APPLICATIONS OF ORGANIC PHOTOREDOX CATALYSIS IN THE DEVELOPMENT OF ALKENE FUNCTIONALIZATION METHODS TOWARD THE SYNTHESIS OF α–BENZYLOXYAMINO- AND HALO-LACTONES Public Deposited

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  • March 21, 2019
Creator
  • Cavanaugh, Cortney
    • Affiliation: College of Arts and Sciences, Department of Chemistry
Abstract
  • I. Introduction To Organic Photoredox Catalysis An overview of the photophysical and electrochemical components of organic photoredox catalysis and its applications in alkene functionalization reactions is addressed. II. Synthesis of α-Benzyloxyamino-γ-Butyrolactones Via a Polar Radical Crossover Cycloaddition Reaction The development of a direct catalytic synthesis of substituted α-benzyloxyamino-γ-butyrolactones, beginning from simple oxime acids and alkenes, is discussed. The substituted O-benzyloxime acid starting materials undergo cyclization with oxidizable alkenes, via Polar Radical Crossover Cycloaddition (PRCC) reactions. The catalytic reaction is carried out using an acridinium photooxidant and substoichiometric amounts of a redox-active cocatalyst. The utility of this methodology is demonstrated through the cyclization of 3 oxime acids and 19 oxidizable olefins to generate 21 highly substituted α-amino lactone products. III. Reversing The Regioselectivity Of Halofunctionalization Reactions Through Cooperative Photoredox And Copper Catalysis A novel method for reversing the regioselectivity of classic alkene halofunctionalization reactions is presented. This transformation relies on the implementation of a dual-catalytic system, incorporating the use of an acridinium photoredox catalyst in conjunction with a copper cocatalyst. The utility of the method is demonstrated through the application of chloro- and bromo-functionalization conditions in both an intra- and intermolecular fashion. Over 15 synthetically and biologically relevant halo-lactones are accessed in a highly regioselective fashion.
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  • In Copyright
Advisor
  • Meek, Simon
  • Gagné, Michel
  • Aubé, Jeffrey
  • Leibfarth, Frank
  • Nicewicz, David
Degree
  • Doctor of Philosophy
Degree granting institution
  • University of North Carolina at Chapel Hill Graduate School
Graduation year
  • 2018
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