Palladium-Catalyzed Carbon-Carbon Bond-Forming Reactions with Unactivated Alkyl Electrophiles

Public Deposited

Downloadable Content

Download PDF
Request Version for Screen Reader
Last Modified
  • March 21, 2019
Creator
  • Venning, Alexander
    • Affiliation: College of Arts and Sciences, Department of Chemistry
Abstract
  • I. Cross-Coupling Reactions with Alkyl Electrophiles An overview of the application of alkyl electrophiles in cross-coupling reactions is presented, highlighting the importance of this reactivity and challenges associated therein. Recent advances in alkyl cross-coupling are discussed, from both a process development and mechanistic perspective, to describe the current state of the field. Advances in hybrid organometallic-radical reactivity are also considered, with particular focus on its application in alkyl cross-coupling and perspective on mechanistic analysis. II. Palladium-Catalyzed Ring-Forming Aromatic C-H Alkylation A palladium-catalyzed, intramolecular aromatic C-H alkylation with unactivated alkyl halides is described. This process is successful with both iodides and bromides, including those with β-hydrogen atoms present. It also tolerates both electron-rich and electron-poor aromatic rings, as well as heteroaromatic substrates. The mild, palladium-catalyzed approach displays compatibility with a diverse range of functional groups, including those which are base- or nucleophile-sensitive. A mechanistic investigation is also presented, suggesting the presence of radical intermediates. III. A Versatile, Palladium-Catalyzed Approach to Alkene-Alkyl Halide Coupling A method for the palladium-catalyzed coupling of alkyl halides with alkenes is presented. Reaction conditions determine whether the end product retains the alkyl halide moiety in an atom-transfer radical cyclization (ATRC) reaction, or if the alkene component is restored, affecting a formal Heck-type transformation. The manifold is capable of performing both transformations with unactivated alkyl bromides and a variety of terminal, di- and tri-substituted alkenes under argon atmosphere. It also enables formation of both 5- and 6-membered rings. A mechanistic investigation of this reaction is presented, which suggests the operation of a catalytic, hybrid organometallic-radical process.
Date of publication
Keyword
DOI
Resource type
Rights statement
  • In Copyright
Advisor
  • Aubé, Jeffrey
  • Alexanian, Erik
  • Gagne, Michel
  • Miller, Alexander
  • Nicewicz, David
Degree
  • Doctor of Philosophy
Degree granting institution
  • University of North Carolina at Chapel Hill Graduate School
Graduation year
  • 2017
Language

Relations

Parents:

This work has no parents.

Items

Thumbnail Title Date Uploaded Visibility Actions
file details Venning_unc_0153D_16925.pdf 2019-04-09 Public Download
file details PREMIS_Events_Metadata_0_2d8a3917-a303-4420-af17-8cf9e3faefcb.txt 2019-04-09 Public Download
file details original_metadata_file_2d8a3917-a303-4420-af17-8cf9e3faefcb.xml 2019-04-09 Public Download