EXPLORING CHEMICAL TRANSFORMATIONS MEDIATED BY SINGLE-ELECTRON OXIDATION: HYDRODECARBOXYLATION, ALKENE-DIFUNCTIONALIZATION, AND HOMOBENZYLIC C-H OXIDATION Public Deposited

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  • March 20, 2019
Creator
  • Griffin, Jeremy
    • Affiliation: College of Arts and Sciences, Department of Chemistry
Abstract
  • Inspired by nature, chemists have strived to promote chemical reactions using visible light. The field of photoredox catalysis has matured from the early stages of being a mere curiosity concerning mainly physical chemists to being a synthetically useful class of reactions. Although photoredox methodologies are not yet widely used in everyday experiments carried out by the average chemist, the use of these technologies are on the rise. This is in part due to their unique ability to enable new reaction manifolds not accessible by many polar reactions. The Nicewicz lab has developed a suite of methodologies so far using organic photoredox catlaysts. Three new methodologies will be described in the following chapters, preceded by a brief discussion on vital aspects of photochemistry. All of the methods described herein are hallmarked by the production of radical intermediates which undergo unique reactivity. A method for hydrodecarboxylation directly from carboxylic acid substrates is described, which is applicable to unactivated substrates. A new strategy for alkene difunctionalization enables the reversal of classic halofunctionalization reactions. Finally, a selective alkane C–H oxidation is in the process of being developed, which has so far been shown to be selective for homobenzylic C–H bonds. Along the way investigations in the reaction mechanisms of each of these methods will also be outlined.
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  • In Copyright
Advisor
  • Dempsey, Jillian
  • Nicewicz, David
  • Miller, Alexander
  • Johnson, Jeffrey
  • Meek, Simon
Degree
  • Doctor of Philosophy
Degree granting institution
  • University of North Carolina at Chapel Hill Graduate School
Graduation year
  • 2018
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