Design of Reagents and Ligands for Direct Palladium-Catalyzed C(sp³)–H Functionalization of Aliphatic Carboxylic Acids

Carboxylic acid directed C–H functionalization reactions have garnered substantial attention over the past few decades. While C–C bond-forming reactions have been extensively explored, C–heteroatom bond-forming reactions remain comparatively underdeveloped. This thesis consists of five chapters, the majority of which describe the development of new strategies for constructing C–heteroatom bonds, along with highlighting potential future directions. Chapter 1 provides an overview of various activation modes employed for the functionalization of C(sp3)–H bonds using carboxylic acids as directing groups. Chapter 2 describes the development of a direct C(sp3)–H fluorination strategy, enabled by the rational design of an oxidizing reagent, marking a conceptual advancement in C–H activation. Building on this concept, Chapter 3 presents a C(sp3)–H hydroxylation method, offering access to a broad range of hydroxy acids via direct C–OH reductive elimination. Chapter 4 details a one-step protocol for accessing γ-lactones via challenging distal C–H activation, in which a new β-alanine derived ligand enabled functionalization of previously inaccessible substrate scaffolds. Finally, Chapter 5 concludes with a description of a molecular stitching approach to access γ-alkylidene lactones, facilitated by a sulfonamide-derived ligand.

Level thesis:degree_level

thesis.doctoral

Grantor dc:publisher

Christian-Albrechts-Universität zu Kiel

Year

2026

Author dc:creator

• Mal, Sourjya

Contributors dc:contributor

• van Gemmeren, Manuel
• Lindhorst, Thisbe

• Aliphatic Carboxylic Acids
• C–H Activation
• Ligand Design
• Palladium
• Lactone
• Fluorination
• Hydroxylation

Repository record source_url

https://macau.uni-kiel.de/receive/macau_mods_00008177

OAI identifier oai:identifier

oai:macau.uni-kiel.de:macau_mods_00008177