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

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.

Name thesis:degree_name

M.S.

Level thesis:degree_level

Thesis

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois Urbana-Champaign

Year dc:date

2025

Author dc:creator

• Hartmann, Marc A.

Contributors dc:contributor

• White, M. Christina

• Catalysis
• Methodology
• Mechanism

Statement dc:rights

• Copyright 2025 Marc Hartmann

Language dc:language

en, eng

Handle dc:identifier

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

OAI record oai:identifier

https://www.ideals.illinois.edu/oai-pmh?verb=GetRecord&metadataPrefix=etdms&identifier=oai%3Awww.ideals.illinois.edu%3A2142%2F129787