2026-09-22T15:40:14Z https://www.ideals.illinois.edu/oai-pmh

oai:www.ideals.illinois.edu:2142/129787 2026-02-10 col_2142_5131 col_2142_14789 com_2142_5130 com_2142_14788 com_2142_8903

application/pdf en text Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2027-05-01 The student, Marc Hartmann, accepted the attached license on 2025-05-07 at 22:41. The student, Marc Hartmann, submitted this Thesis for approval on 2025-05-07 at 22:57. This Thesis was approved for publication on 2025-05-08 at 17:59. DSpace SAF Submission Ingestion Package generated from Vireo submission #22263 on 2025-10-19 at 19:55:50 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. 2025-05-08 White, M. Christina Catalysis Methodology Mechanism eng 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. 2025-05 Text https://hdl.handle.net/2142/129787 Copyright 2025 Marc Hartmann Chemistry Chemistry University of Illinois Urbana-Champaign M.S. Thesis