University of Illinois Urbana-Champaign

Mechanistic investigations into the origin of chemoselectivity a methylene (csp3) c-h oxidation in the presence of α-β unsaturated carbonyls and exploration of reaction scope

Hartmann, Marc A.

This item's files can only be accessed by the System Administrators group.

Permalink

https://hdl.handle.net/2142/129787

Description

Title
Mechanistic investigations into the origin of chemoselectivity a methylene (csp3) c-h oxidation in the presence of α-β unsaturated carbonyls and exploration of reaction scope
Author(s)
Hartmann, Marc A.
Issue Date
2025-05-08
Director of Research (if dissertation) or Advisor (if thesis)
White, M Christina
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois Urbana-Champaign
Degree Name
M.S.
Degree Level
Thesis
Keyword(s)
  • Catalysis
  • Methodology
  • Mechanism
Abstract
α-β unsaturated carbonyls are a common structural motif in bioactive natural products and pharmaceuticals. Despite this, methods for (Csp3) C-H to C-O transformations in the presence of this oxidatively sensitive functionality are underexplored and limited exclusively to radical based methods that target the homolytically weak allyic C-H bonds. Recently, our group developed the first method for (Csp3) C-H in the presence of α-β unsaturated carbonyls enabling rapid access to metabolites and analogues of drugs and complex natural products. This thesis documents mechanistic studies designed to uncover the origin of chemoselectivity for strong bond (Csp3) C-H oxidation over epoxidation of the α-β unsaturated carbonyl π system. Through this process, it was discovered that our new Mn(PDP)/HFIP system has a different active oxidant compared to previous our Mn(PDP)/MeCN/ClAcOH system, which is largely responsible for the enhanced chemoselectivity. Additionally, the generality of our method was accessed on both simple and complex α-β unsaturated carbonyl containing compounds.
Graduation Semester
2025-05
Type of Resource
Thesis
Handle URL
https://hdl.handle.net/2142/129787
Copyright and License Information
Copyright 2025 Marc Hartmann

Owning Collections

Graduate Dissertations and Theses at Illinois PRIMARY
Graduate Theses and Dissertations at Illinois