Organic Chemistry Commons^™

Synthesis Of Oligosaccharide Mimetics By The Desulfurative Rearrangement Of Allylic Disulfides And Stereoelectronic Influence Of C-O Bonds On C- And O-Glycosylation, Myriame Moume-Pymbock

Wayne State University Dissertations

This dissertation focuses on two different problems. The first part of this manuscript presents the application of a novel methodology to access the synthesis of oligosaccharide mimetics while the second part focuses on the study of the stereoelectronic effects of proximal C-O bonds in C- and O-glycosylation reactions.

The first chapter provides a brief overview of the important roles that oligosaccharides and glycoconjugates play in biological processes and sets out the major advances that have been made in the past few decades in the synthesis of such complex structures while bringing out the ongoing challenges and the limitations that impede …

Composition And Antimicrobial Activity Of The Essential Oil Of Hyssopus Seravschanicus Growing Wild In Tajikistan, Rachel M. Thompson, Prabodh Satyal

Summer Community of Scholars Posters (RCEU and HCR Combined Programs)

No abstract provided.

Natural Antiparasitic Coumarins: An In Silico Study, William R. Erwin

Summer Community of Scholars Posters (RCEU and HCR Combined Programs)

No abstract provided.

A Chemical Ecological Investigation Of The Allelophatic Potential Of Lamium Amplexcaule And Lamiun Purpureum, Chelsea D. Jones, Katherine E. Woods

Summer Community of Scholars Posters (RCEU and HCR Combined Programs)

No abstract provided.

Iron(Iii) Tosylate Catalyzed Acylation Of Alcohols, Phenols, And Aldehydes, Ram Mohan, Neil Baldwin, Anna Nord, Brendan O’Donnell

Scholarship

Iron(III) p-toluenesulfonate (tosylate) is an efficient catalyst for acetylation of alcohols, phenols, and aldehydes. The acetylation of 1° and 2° alcohols, diols, and phenols proceeded smoothly with 2.0 mol % of catalyst. However, the reaction worked well with only a few 3° alcohols. The methodology was also applicable to the synthesis of a few benzoate esters but required the use of 5.0 mol % catalyst. Aldehydes could also be converted into the corresponding 1,1-diesters (acylals) under the reaction conditions. Iron(III) tosylate is an inexpensive, and easy to handle, commercially available catalyst.

A Discovery-Oriented Approach To Solid-Phase Peptide Synthesis, Brian Brennan, Matthew Bockman, Christopher Miedema

Scholarship

In this discovery-oriented laboratory experiment, students use solid-phase synthesis techniques to construct a dipeptide containing an unknown amino acid. Following synthesis and cleavage from the polymeric support, electrospray ionization-mass spectrometry is employed to identify the unknown amino acid that was used in the peptide coupling. This experiment, performed in two, 3-h laboratory periods, provides an opportunity for students to learn the technique of solid-phase peptide synthesis and to critically evaluate data that they generate in the laboratory. The experiment is suitable for second-semester organic chemistry students as they learn methods for the formation of amide bonds or upper-level biochemistry students …

Synthesis And Flame Retardant Testing Of New Boronated And Phosphonated Aromatic Compounds, Vladimir Benin, Sravanthi Durganala, Alexander Morgan

Chemistry Faculty Publications

The present report describes the preparation and use of some dimethyl terephthalate derivatives in transition metal-catalyzed coupling reactions to produce new reactive flame retardants. Dimethyl iodoterephthalate and dimethyl 2,5-diiodoterephthalate were successfully employed in the preparation of phosphonic and boronic esters and acids. The latter were tested for heat release with a microcombustion calorimeter (ASTM D7309) to determine the potential for heat release reduction of these flame retardant molecules. The results showed that the addition of boronic or phosphonic acids greatly lowered the heat release, due to a condensed phase (char formation) mechanism. Adding ester groups to the boronic acids or …

Donor-Sigma-Acceptor (D-Sigma-A) Molecules With Perylenebisimide Acceptors Having Alkyl Or Peg Swallowtails With Sulfur Or Hydroxyl Anchors: Synthesis And Applications In Langmuir-Blodgett Films, Single Molecule Spectroscopy (Sms), G-Quadruplex Studies And Passivation Of Gold Nanoparticles, Rajesh Kota

Electronic Theses and Dissertations

Use of single molecules as electronic devices is presently considered a potential alternative to semiconductor-based nanoscale electronics. The ability to study a single molecule or a small group of molecules provides a great opportunity to build electronic devices at the molecular level. It is vital to understand the parameters that control the device properties such as molecular structure, conformation and arrangement at the surface. Ari Aviram and Mark A. Ratner proposed the construction of a single organic molecule as an organic rectifier. Donor-Sigma-Acceptor (D-?-A ) molecules, when arranged with a proper orientation as Langmuir-Blodgett (LB) films and fixed between two …

Isotopic Characterization Of Aerosol Organic Carbon Components Over The Eastern United States, Andrew S. Wozniak, James E. Bauer, Rebecca M. Dickhut, Xu Li, Ann P. Mcnichol

Chemistry & Biochemistry Faculty Publications

Carbon isotopic signatures (δ¹³C, Δ¹⁴C) of aerosol particulate matter total organic carbon (TOC) and operationally defined organic carbon (OC) components were measured in samples from two background sites in the eastern U.S. TOC and water-soluble OC (WSOC)δ¹³C values (−27 to −24‰) indicated predominantly terrestrial C₃ plant and fossil derived sources. Total solvent extracts (TSE) and their aliphatic, aromatic, and polar OC components were depleted in δ¹³C (−30 to −26‰) relative to TOC and WSOC. Δ¹⁴C signatures of aerosol TOC and TSE (−476 to +25‰) suggest variable fossil contributions (∼5–50%) …

Compositional Features Of Japanese Humic Substances Society Standard Soil Humic And Fulvic Acids By Fourier Transform Ion Cyclotron Resonance Mass Spectrometry And X-Ray Diffraction Profile Analysis, Kosuke Ikeya, Rachel L. Sleighter, Patrick G. Hatcher, Akira Watanabe

Chemistry & Biochemistry Faculty Publications

The composition of humic acids (HAs) and Fulvic Acids (FAs) from Inogashira (Umbric Andosol) and Dando (Dystric Cambisol) soils authorized as standard samples by the Japanese Humic Substances Society was characterized using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and X-ray diffraction (XRD) 11 band profile analysis. In FTICR-MS, the number of peaks that molecular formulas were assigned to was 2549-2913 for the FAs and 1943-2457 for the HAs. Molecular formulas with H/C and O/C ratios similar to condensed hydrocarbons were dominant in both the HAs, while those with H/C and O/C ratios similar to lignin were more abundant …

Effects Of Ions On The Activity Of Peptidyl-Trna Hydrolase, Blake Holloway

Summer Community of Scholars Posters (RCEU and HCR Combined Programs)

No abstract provided.

Measuring Antioxidant Properties Through Frap, Xanthine Oxidase, And Orac Assays, Christina Lee

Summer Community of Scholars Posters (RCEU and HCR Combined Programs)

No abstract provided.

Novel Aromatic Ion–Pairs: Synergy Between Electrostatics And Π-Face Aromatic Interactions, Pramod Prasad Poudel

Theses and Dissertations--Chemistry

This dissertation focuses on the design and study of charged aromatic molecules where weak π-π interactions synergize with electrostatic interactions to enhance the overall interaction between aromatic moieties. Each chapter investigates some aspect of this hypothetical synergy between electrostatics and π-face aromatic cohesion.

The first chapter unveiled the importance of electrostatics in the intramolecular stacking of flexible aromatic molecular templates 1-2Br and 2a. While our previous studies found dicationic molecular template 1-2Br to have intramolecular π-stacking between electron poor pyridinium and electron rich xylylene moieties, no such stacking interaction was observed in the neutral analog 2a.

Chapter two systematically …

Development Of Novel Chemical Tools For Proteasome Biology & A New Approach To 1-Azaspirocyclic Ring System, Lalit Kumar

Theses and Dissertations--Chemistry

The proteasome, a multiprotease complex, is clinically validated as an anticancer target by the FDA approval of bortezomib and carfilzomib for the treatment of multiple myeloma. The emergence of resistance to proteasome inhibitors however remains a major clinical challenge. Recently, distinct types of proteasomes termed ‘intermediate proteasomes’, which contain unconventional mixtures of catalytic subunits, have been implicated with drug resistance of tumor cells. In elucidating the role of intermediate proteasomes in drug resistance, a crucial step is to unequivocally determine the subunit composition of intermediate proteasomes in cells. With this in mind, the goal of the studies reported in this …

2- Bromophenyl Salicylate, Donovan Thompson, Sierra Mitchell, Kevin Clarke, Kerry Sarden, Karelle Aiken

Chemistry: Faculty Publications (1990-2023)

2-Bromophenyl salicylate is synthesized from 2-benzyloxybenzoic acid in two steps. The final compound has been characterized by IR,¹H-NMR, ¹³C-NMR and HRMS. The melting point for 2-bromophenyl salicylate is provided.

Asymmetric Intra- And Intermolecular Cyclopropanation By Co(Ii)- Based Metalloradical Catalysis, Xue Xu

USF Tampa Graduate Theses and Dissertations

Metal-catalyzed cyclopropanation of olefins with diazo reagents has attracted research interest because of its fundamental and practical importance. The resulting cyclopropyl units are recurrent motifs in biologically important molecules and can serve as versatile precursors in organic synthesis. Since they were first introduced in 2004, Co(II) complexes of D₂-symmetric chiral amidoporphyrins [Co(D₂-Por*)] have emerged as a new class of catalysts for asymmetric cyclopropanation. These metalloradical catalysts have been shown to be highly effective for asymmetric intermolecular cyclopropanation of a broad scope of substrates with different classes of carbene sources, particularly including electron-deficient olefins and acceptor/acceptor-substituted …

Drug Discovery From Floridian Mangrove Endophytes, Jeremy Beau

USF Tampa Graduate Theses and Dissertations

A significant challenge of the 21st century is the growing health threat stemming from drug-resistant infectious diseases. There is an undeniable need to discover new, safe and effective drugs with novel mechanisms of action to combat this threat. A study of drugs currently on the market showed that natural products account for approximately 75% of new anti-infective drugs, either as new agents or analogs based upon their structure. Unfortunately, major pharmaceutical companies have cut back tremendously in natural products research in part due to the frustrating obstacle of frequent rediscovery of compounds. Fungi in particular are difficult to work with …

Synthesis And Anti-Mrsa Activity Of Hydrophilic C3-Acylated N-Thiolated Β-Lactams And N-Acyl Ciprofloxacin-N-Thiolated Β-Lactam Hybrids, Biplob Bhattacharya

USF Tampa Graduate Theses and Dissertations

The Turos laboratory has been working with N-thiolated β-lactams for years trying to understand the mode of action and structural features it needs to have biological activity. Over the years new data has shown promising inhibitory activity against various microbes.

In this dissertation, a review of the vast amount of work carried out on N-thiolated β-lactams in Turos laboratory has been done and their novelty, in terms of structure and mechanism has been discussed. A complete outline of our work in the discovery and ongoing development of these compounds, starting from our initial, unexpected finding of antimicrobial activity for one …

Chiral Binol Metal Phosphate/Phosphoric Acid Catalyzed Enantioselective Addition Of Phosphorus And Sulfur Nucleophiles To Imines And Epoxides, Gajendrasingh Ingle

USF Tampa Graduate Theses and Dissertations

The research presented in this dissertation focuses on chiral BINOL metal phosphatephosphoric acid catalyzed enantioselective additions of phosphorus and sulfur nucleophiles to imines and epoxides. In chapter 2, we reported a new method to synthesize chiral amino phosphine oxides. The reaction combines N-substituted imines and diphenylphosphine oxide catalyzed by chiral magnesium 9-antryl phosphate. A wide variety of aliphatic and aromatic aldimines substituted by electron neutral benzhydryl or dibenzocycloheptene groups were excellent substrates for the addition reaction. The imines protected with dibenzocycloheptene protecting group provided better enantioselectivity than those protected with benzhydryl group, while both imines gave comparable yields. Also, …

Development And Optimization Of Kinetic Target-Guided Synthesis Approaches Targeting Protein-Protein Interactions Of The Bcl-2 Family, Sameer Shamrao Kulkarni

USF Tampa Graduate Theses and Dissertations

Kinetic target-guided synthesis (TGS) and in situ click chemistry are among unconventional discovery strategies having the potential to streamline the development of protein-protein interaction modulators (PPIMs). In kinetic TGS and in situ click chemistry, the target is directly involved in the assembly of its own potent, bidentate ligand from a pool of reactive fragments. Herein, we report the use and validation of kinetic TGS based on the sulfo-click reaction between thio acids and sulfonyl azides as a screening and synthesis platform for the identification of high-quality PPIMs. Starting from a randomly designed library consisting of nine thio acids and nine …

Enantioselective Brønsted And Lewis Acid-Catalyzed Reaction Methodology: Aziridines As Building Blocks For Catalytic Asymmetric Induction, Shawn E. Larson

USF Tampa Graduate Theses and Dissertations

Chiral molecules as with biological activity are plentiful in nature and the chemical literature; however they represent a smaller portion of the pharmaceutical drug market. As asymmetric methodologies grow more powerful, the tools are becoming available to synthesize chiral molecules in an enantioselective and efficient manner.

Recent breakthroughs in our understanding of phosphoric acid now allow for Lewis acid catalysis via pairing with alkaline earth metals. Using alkaline earth metals with chiral phosphates is an emerging approach to asymmetric methodology, but already has an influential record.

The development of new conditions for the phosphoric acid-catalyzed highly enantioselective ring-opening of meso-aziridines …

Development Of A Bio-Molecular Fluorescent Probe Used In Kinetic Target-Guided Synthesis For The Identification Of Inhibitors Of Enzymatic And Protein-Protein Interaction Targets, Katya Pavlova Nacheva

USF Tampa Graduate Theses and Dissertations

Abstract

Fluorescent molecules used as detection probes and sensors provide vital information about the chemical events in living cells. Despite the large variety of available fluorescent dyes, new improved fluorogenic systems are of continued interest. The Diaryl-substituted Maleimides (DMs) exhibit excellent photophysical properties but have remained unexplored in bioscience applications. Herein we present the identification and full spectroscopic characterization of 3,4-bis(2,4-difluorophenyl)-maleimide and its first reported use as a donor component in Forster resonance energy transfer (FRET) systems. The FRET technique is often used to visualize proteins and to investigate protein-protein interactions in vitro as well as in vivo. The analysis …

Synthesis And Investigation Of The Liquid Crystalline Properties Of Polycyclic Aromatic Hydrocarbons, Joseph A. Paquette

Theses and Dissertations (Comprehensive)

In this thesis, the synthesis and liquid crystalline properties of a series of novel substituted dibenz[a,c]anthracenes is reported. Specifically, a series of hexaalkoxydibenz[a,c]anthracenes were prepared and found not to exhibit a mesophase. In contrast, when substituents are introduced on the aromatic core, columnar mesophases are observed over broad temperature ranges. A series substituted derivatives was prepared and their mesomorphic properties compared. In general, electron-withdrawing substituents promote broad mesophase temperature ranges, as do larger substituents. The liquid crystalline phase is a result of the electronic effects, size and shape of the substituents in the 10 and 13 positions.

We also synthesized …