Development of Fe-Mediated Decarboxylation through Visible Light-Induced Homolysis Restricted; Files Only
Lin, Jung-Ying (Fall 2025)
Abstract
Catalysis has dramatically improved the quality of human life, influencing fields from material science to medicine. To produce these essential molecules precious metal catalysis has played a pivotal role in the toolbox of synthetic reactions over the past decades. However, growing environmental concerns, driven by global warming and population expansion, have recently motivated the exploration of sustainable catalysis. Developing greener strategies, including employing earth-abundant metals as economic and ecological alternatives to precious metals and transforming readily available feedstocks into high-value chemicals, represents a promising direction in synthetic chemistry. Although catalysis based on earth-abundant metals has traditionally been challenging to harness, advances in ligand screening and analytical tools can help unlock their full potential.
This dissertation aims to develop sustainable approaches to facilitate decarboxylation, which can utilize abundant carboxylic groups as coupling handles. Specifically, the reactivity of Fe catalysts which under irradiation can promote decarboxylation through visible light-induced homolysis (VLIH) are employed. Chapter 2 introduces a Fe VLIH decarboxylative Giese reaction, which facilitates the formation of valuable C(sp3)–C(sp3) bonds with generalized reactivities. An unprecedented aliphatic amine ligand demonstrates its utility in improving the reaction yields and spans a much wider redox window of Fe catalysts. Chapter 3 explores the potential mechanism of the Fe-mediated decarboxylative Giese reaction through mononuclear Fe carboxylate photocatalysts. Fe carboxylate complexes containing distinct electronic carboxylates are isolated, which provide valuable structural insights to guide future catalyst design and demonstrate decarboxylation potential for the challenging trifluoroacetate and benzoate. Computational studies support these Fe carboxylate complexes can undergo decarboxylation under visible-light irradiation. Furthermore, the regeneration of the Fe carboxylate complex has been demonstrated. Chapter 4 enables trifluoromethylation on aromatic ring through Fe-mediated decarboxylation under light. Chapter 5 merges Fe VLIH decarboxylation with Ni-catalyzed cross-coupling to establish a sustainable metallaphotoredox catalysis. By leveraging earlier insights, an amine ligand enabling generalized reactivity toward unactivated carboxylic acids is identified. Chapter 6 discusses the need to balance efficient discovery of reaction conditions with a deeper understanding of underlying mechanisms. To enhance insight into catalyst mixtures, a preliminary study explores the use of thermodegradation profiles of metal–ligand mixtures to identify similar pre-stirred solutions. This approach has shown promising correlations with reaction yields, offering a potential approach to expediting catalyst screening and optimization.
Table of Contents
Chapter 1: Development of Sustainable Fe-Mediated Decarboxylation 1
1.1 Significance of Developing Sustainable Catalysts 1
1.2 Decarboxylation using Traditional Precious-Metal Catalysis 2
1.3 Decarboxylation using Fe Photocatalysts through Visible Light-Induced Homolysis 8
1.4 General Proposal of Fe-Mediated Decarboxylation through Visible Light-Induced Homolysis 11
Chapter 2: Development of the Fe-Mediated Decarboxylative Giese Reaction through Visible Light-Induced Homolysis 13
2.1 Introduction and Limitations to the Giese Reaction 13
2.2 Optimization of the Fe-Mediated Photodecarboxylative Giese Reaction 16
2.3 Application of the Fe-Mediated Photodecarboxylative Giese Reaction to Various Carboxylic acids and Electron-Deficient Alkenes 21
2.4 Conclusion 27
2.5 Distribution of Credit 27
2.6 Licenses and Permissions 28
2.7 Experimental Procedures 28
Chapter 3: Elucidating the Mechanism of an Fe-Mediated Decarboxylative Giese Reaction through Visible Light-Induced Homolysis from Mononuclear Fe Carboxylate Complexes 94
3.1 Mechanistic Importance of Fe-Mediated Photodecarboxylation 94
3.2 Synthesis and Characterization of Mononuclear Fe Carboxylate Complexes 99
3.3 Photoreactivity Studies of Fe Carboxylate Complexes 106
3.4 Radical Mechanism Discussion of Fe-Mediated Decarboxylative Giese Reaction 113
3.5 Formation of the Giese Product and Catalyst Regeneration 114
3.6 Proposed Mechanism 116
3.7 Conclusion 117
3.8 Distribution of Credit 118
3.9 Experimental Procedures 118
Chapter 4: Development of Fe-Mediated Photodecarboxylative Trifluoromethylation 286
4.1 Significance of Trifluoromethylation 286
4.2 Optimization of Fe-Mediated Photodecarboxylative Trifluoromethylation 290
4.3 Conclusion 294
4.4 Experimental Procedures 294
Chapter 5: Development of Decarboxylative Cross-Coupling Enabled by Fe and Ni Metallaphotoredox Catalysis 297
5.1 Introduction to Metallaphotoredox Catalysis 297
5.2 Application of Decarboxylative Cross-Coupling to Various Carboxylic Acids and Aryl Halides 300
5.3 Conclusion 307
5.4 Distribution of Credit 308
5.5 Licenses and Permissions 308
5.6 Experimental Procedures 308
Chapter 6: Probing Fe complex Assembly via Thermogravimetric Analysis 388
6.1 Strategy of Reaction Development 388
6.2 Validation of Thermogravimetric Analysis to Support Catalyst Assembly 390
6.3 Conclusion 395
6.4 Distribution of Credit 395
6.5 Licenses and Permissions 396
6.6 Experimental Procedures 396
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File download under embargo until 12 January 2032 | 2025-12-16 18:19:03 -0500 | File download under embargo until 12 January 2032 |
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