TRANSITION-METAL-CATALYZED RADICAL REACTIONS: CARBON-CARBON BOND-FORMING REACTIONS UTILIZING ALKYL ELECTROPHILES
Public Deposited- Last Modified
- March 21, 2019
- Creator
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McMahon, Caitlin
- Affiliation: 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.
- Date of publication
- May 2016
- Keyword
- DOI
- Resource type
- Rights statement
- 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
- Language
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