Organic Chemistry Commons^™

Sulfur Fluoride Exchange With Carbon Pronucleophiles, Joseph R. Novicki, Matthew D. Teeter, Neil J. Baldwin, Christopher W. Am Ende, Alistair D. Richardson, Thomas R. Puleo, Nicholas Ball

Pomona Faculty Publications and Research

Aryl alkyl sulfones are an important class of compounds in drug discovery; thus, new methods toward their synthesis are desirable. A general sulfur fluoride exchange (SuFEx) method to couple aryl sulfonyl fluorides with alkyl carbon pronucleophiles to make aryl alkyl sulfones is described. The reaction was applied to a diverse set of pronucleophiles, including esters, amides, heteroarenes, nitriles, sulfones, sulfoxides, and sulfonamides, at room temperature under mild conditions. We highlight the application of this transformation in parallel medicinal chemistry for the high-throughput generation of a broad array of aryl alkyl sulfones. Lastly, we apply this method to the late-state SuFEx …

Recent Studies On The Reactions And Synthesis Of Nitrogen And Sulfur - Containing Heterocyclic Pharmacophores., Bernard Louis Adjei

Electronic Theses and Dissertations

Nitrogen and sulfur-containing heterocycles remain significant classes of compounds in the field of medicinal and organic chemistry due to their unique structural features and diverse biological activities which make them of considerable interest for drug discovery and development. Notable examples of the nitrogen containing heterocycles include the phthalimide and glutarimide rings present in thalidomide. Thalidomide, a potent small-molecule therapeutic agent, precipitated a significant global drug crisis due to its teratogenicity, causing congenital malformations in phocomelia infants, which remains unrivaled over half a century ago. Currently, thalidomide derivatives are extensively utilized in the therapeutic management of various hematological malignancies. Recent investigations …

Synthetic And Pharmacological Diversity Of Nitrogen-Containing Heterocycles., Shramana Ghosh

Electronic Theses and Dissertations

Nitrogen-containing heterocycles are a foundational class of compounds in organic chemistry, playing critical roles in pharmaceuticals, agrochemicals, and natural products due to their structural diversity and biological relevance. Among them, isoindolinones are notable for their wide range of pharmacological activities. Structurally, isoindolinones possess a benzylic methylene group adjacent to the nitrogen atom, which allows for selective oxidative transformations to yield phthalimide derivatives, well-known intermediates in synthetic, pharmaceutical, and materials chemistry. Although phthalimide is traditionally employed as a protecting group for amines via the Gabriel synthesis, isoindolinone offers a valuable alternative. Through a modified Gabriel-like approach, isoindolinones can serve as more …

Reductive And Nucleophilic Cleavage Of Peroxides And Synthesis Of Tocotrienols As Radioprotective Targets, Amber Marie Schuster

Dissertations and Doctoral Documents, University of Nebraska-Lincoln, 2023–

I. SET CLEAVAGE OF PEROXIDES: INFLUENCE OF REDUCTANT AND PEROXIDE ON THE RATE AND MODE OF ALKOXY RADICAL FORMATION

The reductive cleavage of organic peroxides to generate alkoxy radicals is frequently accomplished via single-electron transfer (SET) from a reductant. Previous reports employ either symmetrical peroxides or peroxides with predictable cleavage behavior, such as peresters. We were interested in how the structure of the peroxide and the nature of the reducing system combine to impact the rate of reaction and the selectivity for alkoxy radical formation during cleavage of unsymmetric peroxides. In this dissertation, one will find the reactions of a …

Aptamer Selection And Development Of Electrochemical Aptamer-Based Sensors For Neuropeptide Y, Evelyn Adela Carreto Guevara

Department of Chemistry: Dissertations, Theses, and Student Research

In this thesis, we report the results of four aptamers obtained from an aptamer selection process called the systematic evolution of ligands by exponential enrichment (SELEX) with affinity to Neuropeptide Y (NPY). NPY is a highly abundant peptide transmitter with widespread distribution throughout the body which affects various physiological functions. These functions include energy homeostasis, appetite regulation, stress response, and anxiety regulation. Dynamic monitoring of NPY levels is crucial for better understanding behaviors in individuals with neurological disorders associated with NPY. Aptamers are synthetic oligonucleotides obtained through SELEX which have a binding affinity to a target of interest when in …

Design And Investigation Of Triarylamine Functionalized Luminophores For Multi-Functional And Stimuli-Responsive Applications, Sasikala R

Theses and Dissertations

Organic solid-state fluorescent materials have garnered attention over many decades in virtue of their contribution in the development of LED devices and biomedical applications. Nevertheless, the potential of fluorescent molecules in device applications was underused due to aggregation-caused quenching (ACQ) effect. The ACQ effect commonly quenches the organic molecules fluorescence intensity in the aggregated or condensed state, which can significantly influence their performance in practical applications.

The organic polyaromatic fluorophores exhibit strong fluorescence in the solution state. After culmination of years of work, Prof. Tang’s research group discovered a new phenomenon of aggregation-induced emission (AIE) in the fluorescence molecules constructed …

Du Undergraduate Showcase Abstracts: Research, Scholarship, And Creative Works, Kabe Aberle, Nadia Kako, Kateri Mcrae, Brooke Agulnek, Sky Palmon, Yasmine Ramirez, Francisca Aguirre Beltran, Ashley Juarez, Bridget Kim, Tessa Appel, Sterling Kerr, Spencer Ingley, Gabe Meyer, Robin Tinghitella, Dale Broder, Lily Baeza, Chloe Beers, Julia Coakley, Whitney Kelsey, Sydney Gainforth, Gabi Wing, Audrey Martin, Aaliyah Amore Berry, Brooke Watley, Kiruthika Venkatesan, Rachel Bienstock, Annabella Brotherston, Madison Bryant, Mia Burgener, Emma P. Lieb, Rachel A. Johnson, Jennifer L. Hoffman, Kania Campbell, Kiena Campbell, Courtney Cassidy, Sage Krzyzkowski, Maddox Jones, Skylar Abookire, Luke Hawkins, Sunnah Yoon, Andrea Chu, Yan Qin, Nyah Cubbison, Brian Gearity, Daniel Mcintosh, Mariely Cruz, Edward Garrido, Grady Dionne, Nicole Doris, Lyndsie Salvagio, Ann-Charlotte Granholm-Bentley, Anna Dymov, Hannah Eckert, Gabrielle Welsh, Erica Larson, Charlie Ernst, Anna Zhou, Sarah Watamura, Larissa Fedorovich-Klein, Georgie Fields, Kimberly A. Guevara, Aven Mccall, Ben Peltier, Feruz Yahia, Patrick Flores, Jadyn Floyd, Sophia Forcier, J. Von R. Monteza, Peter Sokol-Hessner, Gwendolyn Geiger, Scott Nichols, Camryn Gunter, Kendal Hengst, Charlie Bednarz, Issy Garside, Addison Baker, Rachel Mina, Brooke Hermanson, Amanda Klingler, William Highfill, Sydney Jaques, Kerstin Lewey, Allison Grossery, Daniel Linseman, Ethan Lim, Jagger Livengood, Owen Mantelli, Gabby Pappas, Abby Mcdonald, Madeleine Dierking, Eve Miller, Emma Loeber, Anna Marlow, Michael Kerwin, Ella Mathews, Hillary Hamann, Khadija Mohamed, Vivian Nguyen, Gabri Notov, Ifunayachi Ogbonna-Ukuku, Sunil Kumar, Charles Baysah, Sarah Olson, Don Sullivan, Anna Paradiso, Jay Parrish, Mira Pronobis, Alisha Pravasi, Kerstin Haring, Diego Ramirez, Christopher Reardon, Juliana Ramirez, Casey Doherty, Ella Kestner, Teagan Weindel, Cate Billings, Pablo Torre-Walter, Lucy Rand, Samantha Reynolds, Mark Siemens, Khadeeja Rashid, Laine Satterlee, Piper Heilbronner, Lily Pound, Ben Whitehurst, Anna Respet, Lizzie Lesoing, Sydney Hertel, Aya Saad-Masri, Brooke Ballenger, Max Proske, Hannah Rosenberg, Ellia Nakahara, Sophia Espinoza, Ivan Woolhouse, Simon Ruland, Gorkem Er, Timothy Sweeny, Melaku Saketa, Michela Schenk, Maren Lynch, Madi Hamm, Grace Schroeder, Michelle Rozenman, Rana Seif, Jackson Hall, Marisela Simental, Daniel Paredes, Aaron Mena, Preston Spaan, Evelyn Stovin, David Andrew Swartz, Anh Tran, Daniel Pittman, Luke Farchione, Emily Boyer, Ukari Verner, Lacey Conrad, Jonathan Velotta, James Weiner, Jagger Gossett, Noah Sherry, Sam Proud, Ben Block, Avi Narayana, Zoey Weiss, Alyssa Wilson, Gabrielle Walsh, David Zonana, Keely Wright, Kena Riveria, Lillybelle Deer, Jena Doom, Elysia Davis, Isabelle Yaremenko, Caitlyn Young

DU Undergraduate Research Journal Archive

Abstracts from the DU Undergraduate Research Showcase.

Structure-Activity Relationships Of Isothiourea And Silicon Phthalocyanine Catalysts, Christian J. Harrison

Theses and Dissertations

Efficient organic synthesis often relies on improving catalyst designs and investigating reaction mechanisms to accomplish feats such as high stereoselectivity, low catalyst loadings, and performing sustainable chemistry. Within the field of organocatalysis, intermolecular interactions between a catalyst and a substrate are a large contributing factor to the control of a reaction, including rate and selectivity. Investigating mechanisms can provide information on the type of intermolecular interactions occurring in the reaction, aiding future reaction and catalyst development. This dissertation will explore two recent projects and how probing intermolecular interactions through simple modifications provides information useful for new catalyst designs and properties. …

The Potential Importance Of Microenvironment On Polymer Bound Chemical Reagents, Nathan Joseph Halsteter

Theses and Dissertations

In this thesis will provide a brief history of polymer bound reagents, their uses, and advancements. The importance of polymer microenvironments will be explored using a model kinetic resolution reaction utilizing polymer bound reagents to observe how changes in a polymer’s microenvironment effects the yield and selectivity of a reaction. It was found that there are copious factors that affect polymer bound reagents, and no direct conclusion could be drawn from the study.

Lighting Up The Cell: Developing A Luminescent Lanthanide Probe For Detecting Rnas, Jonathan Savell

Honors Projects

An anion detecting luminescent probe, Tb:DO2A-Cs124, was repurposed for use in RNA imaging. Potential RNA aptamers were identified for the molecule using Capture-SELEX and MinION sequencing. Fluorimetry data revealed these aptamers did not allow for the probe to luminesce in the presence of target RNAs due to adenosine monophosphate’s ability to quench the emission signal.

Asymmetric, Carboxy And Ester Functionalized Fluorophthalocyanines: Synthesis, Adsorption, And Reactivity, Sean J. Scally

Seton Hall University Dissertations and Theses (ETDs)

Strong electron-deficient compounds, fluorinated metal phthalocyanines (F_xPcM), exhibit enhanced photosensitizing properties, making them optimal candidates for photocatalytic studies. Perfluoroalkyl-substituted phthalocyanines are notably thermally robust materials that are chemically inert and resistant to electrophilic, nucleophilic, and radical, including reactive oxygen species (ROS) attacks. These properties can be attributed to their ‘Teflon-like’ inert organic shield that surrounds a reactive metal center, as well as their complete (x = 16, 40, 64), or almost complete (x = 48) lack of C-H bonds. Third-generation, functionalized, asymmetric phthalocyanines are of interest due to their ability to bind to oxidic supports via a carboxyl …

Complementary Design Of Optical And Photochemical Systems, Joshua Plank

Chemistry Theses and Dissertations

The ability to manipulate chemical systems has been prized through history as the bridge between the macroscopic and microscopic worlds. As an example, the camera obscura has arguably existed since the earliest days of humanity; however, it was the discovery of early silver halide chemistry that lead to the ability to fix these images into the earliest photographs. In modern photolithography employed in electronics manufacturing, the primary resolution limits arise not from the chemistry of the molecules involved, but from the limits of the systems used to project light. Thus, as much as photochemistry advances, optical imaging and projection techniques …

Bio-Based Composites With Enhanced Mechanical Strength And Flame Retardancy, Riya Patel

Electronic Theses & Dissertations

Composites are versatile and useful in many fields, including aerospace, automotive, construction, and healthcare, due to their high mechanical strength. It is common practice to synthesize these materials using petroleum-based chemicals. Nonetheless, in the twenty-first century, scientists are more interested in using renewable resources to create composites. The greatest substitute for petroleum-based chemicals is vegetable oil. It has unsaturated double bonds that are modifiable chemically. In the present study, bio-polyol was synthesized using castor oil, an inedible vegetable oil. A ring-opening process was used to modify it and produce castor oil-based polyol. The synthesized castor oil-based polyol was characterized by …

Trade-Off Between Limonene & Geraniol-Based Reprocessable And Non-Reprocessable Epoxy Thermosets: Role Of Aliphatic Diamines In Polymer Networks Design, Priyankkumar Kanubhai Patel

Electronic Theses & Dissertations

The growing demand for sustainable materials, driven by environmental concerns and the rapid depletion of fossil fuels, has garnered significant attention in the fabrication of bio-based epoxy thermosets as renewable alternatives to petroleum-derived thermosetting polymers. The present study focuses on the synthesis and characterization of epoxy prepolymer resins derived from limonene and geraniol via a two-step process, followed by the fabrication of thermally cross-linked flexible epoxy thermoset films using various traditional aliphatic diamine curing agents, namely 1,2-ethylenediamine (EDA), 1,4-butylenediamine (BDA), and 1,6-hexamethylenediamine (HDA). Additionally, the incorporation of cystamine, a disulfide-containing diamine, enabled the formation of a covalent adaptable network through …

Enabling New Synthetic Platforms For Aryne Synthesis With Aryl Thianthrenium Reagents, Riley Augustus Roberts

Dissertations and Theses

The enormous importance of aromatic rings in organic molecules cannot be understated. Aromatic rings are present in the majority of pharmaceuticals, agrochemicals, and consumer products. The way in which these rings are arranged and substituted results in a molecule’s unique properties. Because of this, the current limitations of the chemical methods used to synthesize these molecules results in limited structural diversity and thus missed opportunities for the development of value-added products. To this end, this work demonstrates novel methods of aryne synthesis, aryl thianthrenium synthesis and a unique approach to structural scaffold hopping. The approaches presented herein allow for rapid …

Effects Of Structure Of Mepegn Polymers On Hydroxide Conductivity In Anhydrous Anionic Exchange Membranes, Athan M. Gregory

Honors Theses

Anhydrous hydroxide ion (OH-) conducting polymer electrolytes composed of a 1-methyl-pyrrolidinium (1mp) head group linked to various MePEGn (n = 3, 7, 12) backbones were prepared. We have examined the structure of these anion exchange membranes to observe how the structure of the electrolyte affects the observed ionic conductivity. The structural parameters investigated were polymer length, viscosity, fractional free volume (FFV), and volume fraction of PEG (Vf,PEG), and each polymer varied in these properties. Through a comparison of the conductivity and structural parameters in the MePEGn-based anion electrolytes, we have shown that each of these structural properties weakly affects the …

Bottom-Up Mechanochemical Synthesis Of Nanographene, Sarah Kerr

Honors Theses

This research explores the application of mechanochemistry in the bottom-up synthesis of nanographene, specifically focusing on the mechanochemical Diels-Alder (DA) reaction. The study investigates the effect of different reaction conditions and dienophiles on the mechanochemical DA reaction, aiming to optimize reaction efficiency and yield using a ball mill. The initial trials with a sterically hindered dienophile (2) and an electron-deficient diene experienced repeated failure, while reactions using dienophile (B), a terminal alkyne showed more promising results. Various variables were examined, including reaction time, jar size, ball size, ball number, shaking frequency, liquid-assisted grinding (LAG), heating, and diene to dienophile ratio, …

Typical Electron-Withdrawing Groups Are Ortho, Meta-Directors Rather Than Meta-Directors In Electrophilic Aromatic Substitution, Paul R. Rablen

Chemistry & Biochemistry Faculty Works

Electron-withdrawing groups are traditionally considered meta-directing in aromatic substitution reactions. However, when the pre-existing substituent is a π-acceptor, both experiment and calculation indicate that substantial amounts of ortho as well as meta substitution occur, with very little para reactivity. A simple perturbative MO argument rationalizes this finding. It is therefore suggested that these substituents are best understood as ortho, meta-directors, with a preference for meta, just as electron-donating groups are considered ortho, para-directors, with a preference for para.

Synthetic Efforts Towards An Analog Of Ly426965, Macy Sproles

Honors Theses

The 5-hydroxytryptamine_1A (5-HT_1A) receptor is a key target in the treatment of various neuropsychiatric conditions, and the development of selective antagonists offers promising therapeutic potential.²⁴ This study aimed to develop a synthetic analog of LY426965, a selective 5-HT_1A receptor antagonist. The synthetic route was initiated from dimethyl-2-phenylmalonate, employing pig liver esterase (PLE) as an enantioselective biocatalyst to achieve regioselective hydrolysis of one ester moiety in the malonic diester intermediate.¹⁷ Through a series of stereochemically controlled transformations, a new intermediate was successfully synthesized. Although the target molecule was not obtained, a new compound was synthesized …

A Study Of Ultrafast, Intense-Field Photodynamics In Carbon Dioxide, Carbon Disulfide, And Select Substituted Benzenes, Joshua Edwin Beck

Dissertations and Doctoral Documents, University of Nebraska-Lincoln, 2023–

The study of the photodynamics of molecules in ultrashort pulses of intense radiation continues to be of interest. Electric field strengths in such pulses can approach or exceed the typical electric field strengths binding the electrons to the nuclear framework (ke/a²₀ ≈ 5 × 10⁹ V/cm). The resulting excitation, ionization, and dissociation of molecular targets is of interest in many areas including attosecond science, femtochemistry, atmospheric science, high harmonic generation, and many other fields.

This dissertation investigates the photoionization and photofragmentation behavior of carbon dioxide, carbon disulfide, and the substituted benzenes nitrobenzene, aniline, as …