TRANSITION-METAL-CATALYZED RADICAL REACTIONS: CARBON-CARBON BOND-FORMING REACTIONS UTILIZING ALKYL ELECTROPHILES

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  • March 21, 2019
Creator
  • McMahon, Caitlin
    • College of Arts and Sciences, Department of Chemistry
Abstract
  • I. Alkyl Electrophiles in Cross-Coupling An overview of the importance and challenges of applying alkyl electrophiles to cross-coupling reactions is presented. The current state of alkyl cross-coupling is discussed, focusing on both reaction development and mechanistic investigation. Hybrid organometallic-radical reactivity is also described, along with relevant examples. II. Palladium-Catalyzed Intermolecular Heck-Type Cross-Couplings of Unactivated Alkyl Iodides A palladium-catalyzed, intermolecular Heck-type coupling of alkyl iodides and alkenes is described. This process is successful with a variety of primary and secondary unactivated alkyl iodides as reaction partners, including those with hydrogen atoms in the β position. The mild catalytic conditions enable intermolecular C-C bond formations with a diverse set of alkyl iodides and alkenes, including substrates containing base- or nucleophile-sensitive functionality. III. Manganese-Catalyzed Carboacylation of Alkenes Using Alkyl Iodides A manganese-catalyzed carboacylation of alkenes with alkyl halides and carbon monoxide is described. This reaction forms two C-C bonds in one step resulting in cyclized 5-, 6-, and 7-membered ring products. Primary and secondary unactivated iodides undergo reaction with a variety of alkene substitution patterns, including the formation of all-carbon quaternary centers. The reaction has promising applicability in organic synthesis due to the use of an inexpensive, earth-abundant catalyst and mild reaction conditions under low CO pressure.
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  • In Copyright
Advisor
  • Alexanian, Erik
  • Brookhart, Maurice
  • Waters, Marcey
  • Miller, Alexander
  • Johnson, Jeffrey
Degree
  • Doctor of Philosophy
Degree granting institution
  • University of North Carolina at Chapel Hill Graduate School
Graduation year
  • 2016
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Date uploaded
  • July 5, 2017

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