Application of Organic Photoredox Catalysis in New Reaction Methodology: Synthesis of Butyrolactones via Polar Radical Crossover Cycloaddition and Hydrodecarboxylation of Carboxylic Acids Public Deposited

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  • March 20, 2019
Creator
  • Zeller, Mary
    • Affiliation: College of Arts and Sciences, Department of Chemistry
Abstract
  • Synthesis of Butyrolactones via Polar Radical Crossover Cycloaddition A direct catalytic synthesis of γ-butyrolactones from simple alkene and unsaturated acid starting materials is reported. The catalytic system consists of the Fukuzumi acridinium photooxidant and substoichiometric quantities of a redox-active cocatalyst. Oxidizable alkenes such as styrenes and trisubstituted aliphatic alkenes are cyclized with unsaturated acids via polar radical crossover cycloaddition (PRCC) reactions. This method has been applied to the diastereoselective total synthesis of methylenolactocin and protolichesterinic acid. Hydrodecarboxylation of Carboxylic and Malonic Acid Derivatives A direct catalytic hydrodecarboxylation of primary, secondary, and tertiary carboxylic acids is reported. The catalytic system consists of a Fukuzumi acridinium photooxidant with phenyldisulfide acting as a redox-active cocatalyst. Substoichiometric quantities of Hünig’s base are used to reveal the carboxylate. Use of trifluoroethanol as a solvent allowed for significant improvements in substrate compatibilities, as the method reported is not limited to carboxylic acids bearing α-heteroatom or –phenyl substitution. This method has been applied to the direct double decarboxylation of malonic acid derivatives, which allows for the convenient use of dimethyl malonate as a methylene synthon.
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Rights statement
  • In Copyright
Advisor
  • Nicewicz, David
  • Dempsey, Jillian
  • Johnson, Jeffrey
  • Meek, Simon
  • Brookhart, Maurice
Degree
  • Doctor of Philosophy
Degree granting institution
  • University of North Carolina at Chapel Hill Graduate School
Graduation year
  • 2016
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