Organic Chemistry Commons^™

Synthesis Of Novel 5-Aryl 2’-Deoxyuridine And 2’-Deoxycytidine Analogues, Kevin E. Persaud

Dissertations and Theses

Briefly, the following report details a synthetic route to prepare 5-phenyl-2’-deoxycytidine analogues. This multistep synthesis began with silyl protection of the 3’- and 5’-hydroxyl groups of 5-iodo-2’-deoxyuridine. Next, the installation of a phenyl ring at the C5 position of the nucleobase via a Suzuki-Miyaura cross-coupling reaction, yielding 5-phenyl-2’-deoxyuridine (5-PdU). After that, modification of the obtained 5-PdU at the C4 position was performed with benzotriazole-1-yl-oxy-tris-(dimethylamino)-phosphonium hexafluorophosphate (BOP, a peptide-coupling agent) and a base (cesium carbonate) to activate the amide group of the uridine nucleobase for subsequent displacement with a variety of amines. Modification of the C4 position resulted in protected 5-phenyl-2’-deoxycytidine …

Illuminating Function And Enabling Inhibition At The Protein-Membrane Interface Of Glutathione Peroxidase 4., Courtney L. Labrecque

Theses and Dissertations

Membrane proteins act as gateways to cells and are responsible not only for signaling, lipid transport, and cellular homeostasis, but they are also integral in disease pathologies. One class of membrane proteins, peripheral membrane proteins (PMPs), reside in aqueous compartments of the cell until they are recruited to the membrane to perform their function. Glutathione peroxidase 4 (GPx4) is a PMP enzyme responsible for engaging the membrane and reducing lipid hydroperoxides, thereby preventing cellular death via ferroptosis. Due to its central function surrounding ferroptosis, GPx4 is an interesting drug target that has recently gained interest for inflammatory diseases as well …

Asymmetric Cuh-Catalyzed Reductive Coupling Of Allenamides With Carbonyl And Imine Electrophiles, Stephen Collins

Theses and Dissertations

The carbon scaffold of many drugs and natural products contain multiple stereogenic centers bearing heteroatoms. As a result of this, chemists have long sought methods to efficiently install these multi-heteroatom functionalities. Reductive coupling reactions have been extensively studied over the past decades, and the allylation of carbonyls via the reductive coupling approach has been a key method for generating chiral allylic alcohols. This work utilizes inexpensive Cu for the asymmetric reductive coupling of allenamides with carbonyls or imines to simultaneously install two heteroatoms (either oxygen and nitrogen or nitrogen and nitrogen, respectively) onto the product. These molecules have a polarity …

Synthetic Strategies Toward The Development Of Stable Gold-Based Anticancer Agents And Their Mechanistic Insight, Adedamola Arojojoye

Theses and Dissertations--Chemistry

Despite notable advancements in the design and synthesis of novel chemotherapeutic drugs, cancer continues to be a leading cause of death in the United States. Metallodrugs, especially Au complexes, have played a prominent role in the search for the next generation of chemotherapeutic agents. Herein, I report on the synthetic strategies towards the rational design of stable Au (Au)-based agents, study their reactivity in biological environment, and offer insights into the cytotoxic mechanism of action in cancer. Chemotherapeutic Au compounds exist mainly in +I or +III oxidation states. Repurposing of the Au(I) FDA approved auranofin for the treatment of diseases …

Studies Towards Mechanistic Understanding Of The Suzuki-Miyaura Catalyst-Transfer Polymerization, Mitchell Tyler Howell

Graduate Research Theses & Dissertations

Semiconducting organic conjugated polymers show major promise for the manufacturing of organic electronic and optoelectronic devices. Their utility comes from inherent conductivity, elasticity, processability and low weight paving the way towards novel materials and applications. The molecular weight, polydispersity, and precise incorporation of structural elements into the conjugated backbone are among the important parameters that affect a conjugated polymer’s mechanical and electrical properties. Therefore, precise control over such parameters provides a path for electronic materials with tunable properties tailored for a specific application. Recent success in this endeavor has been achieved with Suzuki-Miyaura Catalyst-Transfer Polymerization (SCTP) which is a transition …

Synthesis Of A Basket-Shaped Host Molecule Based On P-Tert-Butylcalix[4]Arene Featuring Pyridinyl Groups For Volatile Guest Molecule, Boluwatife S. Ajewole

Masters Theses

Supramolecular and Molecular chemistry offer an expanding array of applications for the development of smart devices, with calixarene-based molecular baskets playing a pivotal role in host-guest chemistry. A key concept in this field is the design of "smart" molecules with gate-like features, which can selectively transport chemical or biochemical species that are volatile, reactive, or sensitive to typical solution environments. These molecular hosts are engineered with predefined groups that respond to external stimuli, such as changes in concentration, temperature, or pH.

Molecular baskets are synthetic host molecules designed to capture guest molecules selectively through adjustable gates. In our study, we …

Addition Reactions Of Olefinic Heterocycles And 4-Hydroxycoumarins, Benjamin Goka

Graduate Research Theses & Dissertations

The work outlined in this dissertation describes acid-base catalyzed projects facilitating the construction of key synthetic analogs with vast therapeutic applications. Three major projects have been covered demonstrating various synthetic routes developed by our research group to furnish key derivatives of heterocyclic compounds, including coumarins, carbohydrate moieties, and beta-lactams. By their catalytic nature, acids, and bases are known to enhance the reactivities of compounds. This allows synthetic chemists to design or chart new and better reaction pathways leading to the delivery of desired reaction products. The first chapter features a summary of the main concepts underpinning the projects.

Chapter 2 …

Superelectrophile Promoted Syntheses Of Aromatic Spirocycles, Jeffrey Caz Ferreira

Graduate Research Theses & Dissertations

Aromatic spirocycles are crucial organic scaffolds that are at the forefront of innovation in various fields of organic electronics, as well as in drug design. The synthesis of these compounds is challenging, especially on an industrial scale and often have suboptimal yields in many traditional syntheses. New synthetic methodologies are being continually explored for the installation of sp3 hydridized spiro junctions. Our research group, as well as other groups, have done exploration of using superelectrophilic synthetic routes that are nicely applied to the formation of aromatic spirocycles. Most relevant to the results discussed in this dissertation are condensation chemistry using …

Designing Fluorescent Moscs For Potential Applications In Illicit Drugs Detection, Robyn Nicole Cook

Dissertations and Theses

Illicit and hazardous substances pose a serious effect on the human body which can create longer-term issues on the mental and physical health which potentially lead to fatalities. Current methods for detecting illicit substances include analytical techniques like mass spectrometry (MS) and gas/liquid chromatography (GC/LC) which are known for accuracy and sensitivity. However, these instruments are bulky, costly, time-consuming, and require highly trained personnel. An alternative approach to overcoming these limitations is to employ nanostructured molecule-based chemical sensing technologies that are user-friendly, portable, and cost-effective with the sensitivity for detecting illicit substances. One such candidate is metal-organic super-containers (MOSCs), which …

Hybridization And Duplex Stability Of Peptide Nucleic Acid Containing An Azobenzene Switch, Carmen J. Velasquez

College of Graduate Studies: Theses & Dissertations

Light-driven molecular switches that can be turned on and off on demand have found many biological applications. For DNA, RNA, and synthetic derivatives, the switch can be used to interfere with a hybridization event with a complementary strand. To explore this potential, we have synthesized three light-sensitive PNA which have an azobenzene group (PNA-5azo5 and PNA-4azo4), and two azobenzene groups (PNA-2azo5azo2) as part of the PNA backbone. UV experiments were used to verify the conversion to the cis-isomer from the initial trans state for all of the single-stranded Azo-PNA ( PNA-5azo5, PNA-4azo4, and PNA-2azo5azo2) by irradiating at 365 nm …

Chemical Synthesis Of Sensitive Dna, Komal Chillar

Dissertations, Master's Theses and Master's Reports

Over the past decades, researchers have tried various chemical methods to synthesize modified oligodeoxynucleotides (ODNs, i.e. short segments of DNAs). Traditional ODN synthesis methods require strong basic, and nucleophilic conditions for the deprotection and cleavage of the ODN from the solid support. However, the sensitive ODNs containing labile functionalities are vulnerable to such harsh conditions. Sensitive ODNs have a wide range of applications in research and pharmaceuticals. To synthesize sensitive ODNs, researchers devised different strategies but no practical methods have been developed. To overcome these challenges, we developed alkyl Dim alkyl Dmoc technology. This innovative technology uses weakly basic and …

Extraction Of Capsaicin Using The Polyol Induced Extraction (Pie) Method, Orlando Herrera

All Student Theses and Dissertations

Polyol-induced extraction (PIE) is an extraction technique for separating organic solvents from water, using glycerol and polyol as separating agents. Glycerol binds water releasing the organic solvent as a separate liquid phase. this thesis, investigates how the PIE process may be used to separate caffeine and capsaicin. When acetonitrile and water are used as a 1:1 solvent mixture, two immiscible phases are created upon addition of the polyol, glycerol. Initially, for purposes of training on the PIE method, the studies primarly began with the extraction of pure caffeine. Using a 1:1 mixture of acetonitrile and water, 20 m/v % glycerol, …

Additive-Dependent Regioselective Boracarboxylation Of Alkenes Using Low Valent Copper And Co2, Carly H. Gordon Ph.D.

Graduate Theses, Dissertations, and Problem Reports (ETD)

As a major greenhouse gas, carbon dioxide (CO₂) is an abundant and renewable C₁ feedstock, and developing methods for fixing CO₂ into high-value products is a major interest for the movement of greener chemistry. The boracarboxylation of alkenes provides access to difunctionalized products containing pharmaceutically relevant motifs, including carboxylic acids and boron-containing moieties. Significant work has been done to improve the versatility and efficiency of this methodology, with the recent expansion into a wide variety of terminal alkenes. The use of different phosphine and alkene additives have demonstrated positive effects on reaction rates and productivity, indicating …

Photoinduced Alpha-Hydroxy C–H Alkylation Of Mono-Alcohols Via Hydrogen Atom Transfer (Hat) Of An Activated Boron-Containing Complex, Courtney Deanna Glenn

Graduate Theses, Dissertations, and Problem Reports (ETD)

Hydroxy (-OH) groups are one of the most abundant functional groups found in natural products and pharmaceuticals with many of these compounds containing multiple alcohol classes. The ability to selectively functionalize a specific α-OH C–H bond in the presence of other competitive sites would provide straightforward access to new, potentially bioactive compounds. In recent literature, photoredox catalysis has been implemented to perform site and stereoselective α-OH C–H functionalization of cis-diol containing substrates. Incorporating an organoboron cocatalyst into these systems have proven to be crucial in decreasing the bond dissociation energy (BDE) and increasing hydricity of the α-OH C–H bond …

The Investigation Of The Antimicrobial And Biofilm-Disrupting Properties Of Synthesized Hemibastadin Derivatives, Antonio Harvey, Andrew A. Yeagley

Longwood Senior Thesis Proposal

We want to investigate structural changes to the core hemibastadin structure while attempting to make these derivatives biologically safer. Since these modifications have never been done before, we will need to design a synthesis of these new molecules. Due to the nature of the molecules (dimers), a divergent synthesis that allows for the creation of both halves simultaneously seems most appropriate. A successful synthesis of these compounds will allow us to further investigate these derivatives for their antimicrobial and biofilm-disrupting properties.

Covalent Inhibition Of Enzyme Sortase A As A New Pathway Against Bacterial Resistance Of Staphylococcus Aureus, Umyeena Bashir

Master's Theses

The continued rise of antibiotic-resistant bacteria, such as MRSA (methicillin-resistant Staphylococcus aureus), has made the discovery of novel antibiotics critical. While bacteriostatic and bactericidal antibiotics inevitably exert evolutionary pressure on bacteria to develop resistance, small molecules that target mechanisms of bacterial virulence present a promising alternative for treatment. Sortase A (Srt A), a cysteine protease of S. aureus, promotes bacterial virulence by covalently attaching proteins such as pilin to the bacterial surface, enabling bacterial adhesion to mammalian cells. Inhibitory studies of this enzyme have gained prominent interest as a new pathway for drug development since blocking this enzyme's ability to …

Optimization Of Transition-Metal Inclusive Carbon Aerogels For Electrochemical Energy Applications, Allen Dalton Davis

Electronic Theses & Dissertations

The ever-growing need for energy alongside rising concerns for climate change demands the development of renewable energy technologies. Hydrogen fuel cells are a promising technology that can serve to either supplement energy generation or act as a lone power source. Yet for these devices to be truly green, the hydrogen that serves as fuel must be procured from a renewable resource. Electrolytic water splitting is a process that allows for the dissociation of water into H₂ and O₂. For this process to be practical, the electrolyzer needs to demonstrate high efficiency and stability, as well as a …

Exploring Soybean Oil-Based Polyol And Effect Of Non-Halogenated Flame Retardants In Rigid Polyurethane Foam, Sahithi Kondaveeti

Electronic Theses & Dissertations

To address the increasing demand for sustainable biomaterials due to the depletion of fossil fuel resources and growing environmental concerns, a new type of biodegradable and environmentally friendly rigid polyurethane foam (RPUF) has been synthesized. These foams are derived from chemically modified soybean oil-based polyol obtained from soybean oil by epoxidation followed by a ring-opening reaction. Polyurethane foam is generally used in construction, furniture, and automobile industries but is highly flammable and releases toxic gases and smoke during combustion. In this study, a highly efficient synergistic effect halogen-free flame-retardant (FR) melamine salt, 2-carboxyethyl(phenyl)phosphinic acid melamine salt (CMA) was synthesized from …

Enhanced Mechanical Strength Of Soybean Oil-Based Non-Isocyanate Polyurethane Adhesive For Wood Application By Introducing Nanofillers, Vatsal Chaudhari

Electronic Theses & Dissertations

Polyurethane (PU) is a versatile material that finds extensive use in various industries including bedding, construction, automotive, and packaging. Historically, this particular polymer relied significantly on petrochemical resources, a practice that was considered to have negative environmental impacts. The conventional method for preparing PU involves the use of isocyanate, which is a disadvantage due to its negative impact on the environment and human health. The resolution of this problem entails identifying an appropriate substitute for petroleum-derived products that minimize their impact on both the environment and human health. The researchers earlier utilized soybean oil, for the formulation of PUs in …

Castor Oil Polyol-Based Adhesives With Additional Crosslinker For Improvement In Mechanical And Thermal Properties., Yash Desai

Electronic Theses & Dissertations

Polyurethanes (PU) have been promising polymeric materials with many applications, including adhesives. Projecting an estimated revenue from 42.8 billion $ in 2021 to 61.5 billion $ by 2026. However, a large number of PU adhesives are sourced from petroleum products. Therefore, to lower the dependence on non-renewable resources and provide sustainable and affordable alternatives. In this work will synthesize bio-based adhesives of polyurethane from modified castor oil-based polyol. Generally, polyurethane reaction depends on the properties of polyol and isocyanates. The most important aspect of these reactions is the OH number of the polyol, which is responsible for the crosslinking and …