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Full-Text Articles in Organic Chemistry

An Investigation Of Alkylboron Transmetallation In Palladium-Catalyzed Suzuki Reactions, Benjamin Murray May 2019

An Investigation Of Alkylboron Transmetallation In Palladium-Catalyzed Suzuki Reactions, Benjamin Murray

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Through the past 40 years, carbon-carbon cross-coupling reactions have greatly enhanced the ability of chemists to synthesize C(sp2)-C(sp2) bonds and more recently C(sp2)-C(sp3) bonds. In particular, the Suzuki reaction has proven to be invaluable with its high yields, good functional group tolerance, and low toxicity of reagents. One of the component steps of the catalytic cycle of this reaction is transmetallation, in which the nucleophilic species transfers its organic component to the metal center (generally palladium). The mechanism of transfer from primary alkylboron nucleophiles was studied in the 1990's ...


Preparation Of Enantioenriched Alkyltin Species And Their Application In Stereospecific Transformations, Glenn O. Ralph May 2019

Preparation Of Enantioenriched Alkyltin Species And Their Application In Stereospecific Transformations, Glenn O. Ralph

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Organometallic reagents containing the tin-carbon bond are used extensively in modern synthetic chemistry for the formation of new bonds to carbon. Over recent decades, transition metal catalyzed cross coupling reactions between two C(sp2) centers have been widely developed. However, the introduction of a C(sp3) center complicates the catalytic cycle, and opens unproductive chemical pathways which lead to isomerization, elimination, and racemization. Our lab has developed a modified-Stille reaction to combat the deleterious effects of β-hydride elimination. Our protocol enables unactivated 2° alkyl organotin nucleophiles to undergo efficient cross coupling reactions with C(sp2) electrophiles, avoiding ...


Mild Synthesis Of Perylene Tetracarboxylic Monoanhydrides With Potential Applications In Organic Optoelectronics, Xizhe Zhao May 2019

Mild Synthesis Of Perylene Tetracarboxylic Monoanhydrides With Potential Applications In Organic Optoelectronics, Xizhe Zhao

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Perylene tetracarboxylic derivatives are considered good n-type semi-conductors. In past decades, there has been extensive study on their synthesis and electronic properties. Because of the high electron affinity, the ability to form π-π stacks, they have been widely utilized in organic photovoltaic solar cells, field-effect transistors and light-emitting diodes. Many of those applications prefer unsymmetrically substituted perylene tetracarboxylic derivatives. Perylene monoanhydrides are the most versatile intermediates for the preparation of unsymmetrically substituted perylene tetracarboxylic derivatives. In this thesis, I focused on introducing new synthesis methods for perylene monoanhydrides with labile functional group and their potential applications in organic optoelectronics.

In ...


Bisthioether Stapled Peptides Targeting Polycomb Repressive Complex 2 Gene Repression, Gan Zhang Feb 2019

Bisthioether Stapled Peptides Targeting Polycomb Repressive Complex 2 Gene Repression, Gan Zhang

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Interactions between proteins play a key role in nearly all cellular process, and therefore, disruption of such interactions may lead to many different types of cellular dysfunctions. Hence, pathologic protein-protein interactions (PPIs) constitute highly attractive drug targets and hold great potential for developing novel therapeutic agents for the treatment of incurable human diseases. Unfortunately, the identification of PPI inhibitors is an extremely challenging task, since traditionally used small molecule ligands are mostly unable to cover and anchor on the extensive flat surfaces that define those binary protein complexes. In contrast, large biomolecules such as proteins or peptides are ideal fits ...


A Stereospecific Pd-Catalyzed Suzuki Cross-Coupling Reaction And A Statistical Study Of The Ligand's Role In Stereoselection, Shibin Zhao Sep 2018

A Stereospecific Pd-Catalyzed Suzuki Cross-Coupling Reaction And A Statistical Study Of The Ligand's Role In Stereoselection, Shibin Zhao

All Dissertations, Theses, and Capstone Projects

The development of palladium-catalyzed carbon-carbon cross-coupling reactions has profoundly influenced the manner through which we approach the synthesis of complex organic molecules. Among established cross-coupling reactions, which include Kumada, Negishi, and Stille reactions, the Suzuki cross-coupling reaction exhibits particularly wide functional group compatibility, while employing non-toxic, air-stable organoboron nucleophiles. Conventional studies of Pd-catalyzed Suzuki cross-coupling reactions have focused on C(sp2)-C(sp2) cross-coupling reactions, which result in the formation of planar products. Conceptually, the use of C(sp3) (secondary) nucleophiles would enable the reliable manipulation of organic molecules in three dimensions. However, this process has not ...


Synthesis And Evaluation Of Densely-Functionalized Troponoids, Danielle R. Hirsch Sep 2018

Synthesis And Evaluation Of Densely-Functionalized Troponoids, Danielle R. Hirsch

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Herein, we document our efforts to expand the scope of troponoid synthetic methodology towards densely-substituted scaffolds. This body of work has focused primarily on an oxidopyrylium cycloaddition/ring-opening strategy for the synthesis and biochemical evaluation of troponoids for assistance in a variety of medicinal chemistry studies. In Chapter 1, we outline the use of this synthetic strategy in the profiling of a library of synthetic αHTs against an aminoglycoside antibiotic resistance enzyme known as aminoglycoside-2’’-O-nucleotidyltransferase [ANT(2’’)-Ia]. Enzymatic mechanistic insights have been gleaned from an assessment of troponoid/antibiotic synergistic potential. In particular, two synthetic constructs were identified ...


Organic Photochemistry: Remote Delivery Of Reactive Oxygen Intermediates Via A Heterogeneous Approach, Niluksha Walalawela Abeykoon Feb 2018

Organic Photochemistry: Remote Delivery Of Reactive Oxygen Intermediates Via A Heterogeneous Approach, Niluksha Walalawela Abeykoon

All Dissertations, Theses, and Capstone Projects

Photosensitized oxidation reactions produce a number of intermediates species, which are generated in varying amounts over time. This complexity presents major challenges in the study of oxidation processes. Mechanistic efforts to separate and deliver reactive oxygen intermediates enable their controlled use in processes such as bacterial inactivation. This thesis describes a heterogeneous reaction approach taken to control the generation and delivery of reactive oxygen intermediates. The mechanistic details of photosensitized reactions were elucidated via synthetic, materials, and physical organic techniques to optimize the delivery of reactive oxygen intermediates. This thesis contains six chapters as described below.

Chapter 1 gives a ...


Discovery And Development Of A Three-Component Oxidopyrylium Cycloaddition And Its Application Towards Alpha-Hydroxytropolone Synthesis, Michael P. D'Erasmo Feb 2018

Discovery And Development Of A Three-Component Oxidopyrylium Cycloaddition And Its Application Towards Alpha-Hydroxytropolone Synthesis, Michael P. D'Erasmo

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Historically, natural products have provided unique research opportunities and challenges for organic synthesis, chemical biology, and medicinal chemistry due to their molecular complexity and effects on physiological systems. The total synthesis of natural products has not only produced novel reaction methods and strategies capable of efficiently generating complex structural motifs but also granted access to sufficient quantities of otherwise scarce natural product material for clinical evaluation. These synthetic efforts have facilitated the formation of a transdisciplinary partnership between chemistry, biology, and medicine that has been paramount in elucidating the chemical and pharmaceutical utility of natural products. Chapter I of this ...


Synthesis And Evaluation Of Tetrahydroprotoberberines As Dopamine Receptor Ligands, Satishkumar V. Gadhiya Sep 2017

Synthesis And Evaluation Of Tetrahydroprotoberberines As Dopamine Receptor Ligands, Satishkumar V. Gadhiya

All Dissertations, Theses, and Capstone Projects

Dopamine (DA) receptors belong to the G-protein coupled receptors (GPCRs) family, divided in to two groups based on their high homology transmembrane domains; D1-like DA receptors (D1, D5) and D2-like DA receptors (D2-D4). DA receptor specific ligands have been exploited as a means for studying the prognosis and curing several CNS disorders. Though several efforts have been devoted to discover selective and potent DA receptor ligands, complete selectivity within the DA receptor subtypes remains a challenge.

Tetrahydroprotoberberines (THPBs) are a group of naturally occurring tetracyclic alkaloids that belong to the tetrahydroisoquinoline family. A wide range of biological activities are associated ...


Stereospecific Electrophilic Fluorination Of Alkylcarbastannatrane Reagents, Xinghua Ma Sep 2017

Stereospecific Electrophilic Fluorination Of Alkylcarbastannatrane Reagents, Xinghua Ma

All Dissertations, Theses, and Capstone Projects

The introduction of fluorine atoms into organic molecules significantly changes their physical, chemical, and biological properties. Fluorinated organic compounds are used as pharmaceuticals, agrochemicals, materials, and tracers for positron emission tomography (PET). For example, the site-specific fluorination of drugs can block sites of phase I metabolism by cytochrome P450 enzymes as well as improve target-binding affinities. In view of the unique features of fluorine-containing compounds, there has been increasing interest in the development of novel methods for the synthesis of fluorinated molecules, especially the site-specific monofluorination of complex molecules. Herein, we present the enantiospecific conversion of chiral secondary alkylcarbastannatranes into ...


Olfactory Receptor Antagonism In The Or-I7 Aldehyde Receptor And The Mammalian Olfactory System, Min Ting Liu Jun 2017

Olfactory Receptor Antagonism In The Or-I7 Aldehyde Receptor And The Mammalian Olfactory System, Min Ting Liu

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The detection of smell is initiated when an odorant binds and activates olfactory receptors (ORs) within the nose. Chapter 1 studies the structural requirements for activation of the OR-I7 aldehyde receptor. Octanal is an agonist of the OR-I7 receptor. 4-Ethylcyclohexylacetaldehyde (1.1), with a cyclohexyl ring that locks the C4-C5 bond of octanal in the gauche conformation, was previously found to have higher potency than octanal, suggesting that the OR-I7 receptor prefers the gauche conformation of octanal during activation. However, 1.1 had only been previously tested as a mixture of cis- and trans-isomers, and therefore, it was not ...


From The Making To The Tuning To The Use Of Chlorins For Biomedical Applications, Junior Gonzales Jun 2017

From The Making To The Tuning To The Use Of Chlorins For Biomedical Applications, Junior Gonzales

All Dissertations, Theses, and Capstone Projects

Chlorins are porphyrins missing a double bond. These pigments are optimal platforms for the development of novel dyes that display drug-like attributes such as photodynamic therapy (PDT) agents. More recently, it was demonstrated that chlorins can serve both as a PDT agent and as a modality for fluorescence or PET imaging. Thus, multifunctional chlorins eliminate the differences that may occur in specificity, uptake, and distribution between separate compounds or constructs for imaging and therapy. The overall goal of this dissertation is to take advantage of the reputed intrinsic attributes of chlorins as a viable tool in biomedical applications. In this ...


The Modified Stereospecific Stille Reaction: Palladium-Catalyzed Cross-Coupling Reactions Involving Secondary And Tertiary Alkyl Carbastannatranes, Chao-Yuan Wang Jun 2017

The Modified Stereospecific Stille Reaction: Palladium-Catalyzed Cross-Coupling Reactions Involving Secondary And Tertiary Alkyl Carbastannatranes, Chao-Yuan Wang

All Dissertations, Theses, and Capstone Projects

Organic chemistry is present in all domains of everyday life, from polymer production to medicine. In order to synthesize complex compounds, it is often necessary to make new carbon-carbon bonds. Transition metal catalysts, particularly those derived from second and third row metals such as Pt, Pd, Rh, and Ir metals, display remarkable efficiency for the formation of carbon-carbon and carbon-heteroatom bonds. In the first chapter, introduction of transition metal-catalyzed cross-coupling reactions is given. While the formation of C(sp2)–C(sp2) bonds has been studied extensively, C(sp3)-C(sp2) bond formation still presents a challenge ...


I. Synthesis Of Diverse Structures From Quinone Monoketal And Quinone Imine Ketal With Efficiency And Control Ii. Synthetic Study Of Phalarine, Zhiwei Yin Sep 2016

I. Synthesis Of Diverse Structures From Quinone Monoketal And Quinone Imine Ketal With Efficiency And Control Ii. Synthetic Study Of Phalarine, Zhiwei Yin

All Dissertations, Theses, and Capstone Projects

Quinonoids are quinone derivatives that have carbonyl or carbonyl equivalent and even number of double bonds embedded in six member rings. As a result of the intrinsic α,β-unsaturated ketone or imine structures, quinonoids, such as quinone monoketals, quinols, quinol ethers and quinone imine ketals, can accommodate a wide range of reactions including 1,2-additon, 1,4-addtion, SN2’ reaction (allylic substitution) to the α-carbon of the carbonyl or imine and cycloaddition reactions (e.g. Diels-Alder reaction). Quinonoids are effective building blocks for synthesizing heterocycles, which are ubiquitous in pharmaceutically useful agents. Developing new quinonoid based methodologies is essential to expanding ...


Photodynamic Killing Of Human Cancer Cells With Smart Photosensitizer Materials And An Endoscopic Implement For Singlet Oxygen Delivery, Mihaela N. Minnis Sep 2016

Photodynamic Killing Of Human Cancer Cells With Smart Photosensitizer Materials And An Endoscopic Implement For Singlet Oxygen Delivery, Mihaela N. Minnis

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The thesis describes progress on probe tips for a microoptic device for the precise delivery of the components necessary for photodynamic therapy (PDT) in a highly localized and controllable fashion. The thesis also summarizes results of a photosensitized oxidation study. The work focused on i) developing a photoactive fluoropolymer surface that will release sensitizer drug molecule for use in PDT, ii) designing new probe tips surfaces for use as sensitizer support for a microoptic PDT device, iii) exploring strategies for covalent attachment of sensitizers and model compounds to Teflon/PVA surfaces with the aim of being coupled with our microoptic ...


Photooxidation Chemistry And Photodynamic Therapy: Pointsource Delivery Of Singlet Oxygen, Sensitizer And Nitrosamine Drugs, Ashwini Anil Ghogare Jun 2016

Photooxidation Chemistry And Photodynamic Therapy: Pointsource Delivery Of Singlet Oxygen, Sensitizer And Nitrosamine Drugs, Ashwini Anil Ghogare

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Eradication of residual tumor cells that are directly adjacent to vital tissue is a daunting challenge to surgeons. Because the field needs advances in intraoperative settings and a means for high-precision delivery of singlet oxygen for photodynamic therapy (PDT) of cancers, this dissertation outlines the development and application of a “pointsource” fiber optic device. The device offers highly localized and simultaneous delivery of sensitizer drug, light, and oxygen (components necessary for PDT) for cancer cell eradication in-vitro and in-vivo. The following chapters describe (a) the photokilling activity and precision of pointsource PDT in monolayer ovarian and brain cancer cells in-vitro ...


Ultrafast Spectroscopy And Energy Transfer In An Organic/Inorganic Composite Of Zinc Oxide And Graphite Oxide, Jeff A. Secor Feb 2016

Ultrafast Spectroscopy And Energy Transfer In An Organic/Inorganic Composite Of Zinc Oxide And Graphite Oxide, Jeff A. Secor

All Dissertations, Theses, and Capstone Projects

The energy transfers and nature of defect levels of an organic/inorganic composite of Zinc Oxide and Graphite are studied with multidimensional spectroscopy. The edge and surface states of each composite are uncovered using excitation emission experiments showing which defect states are mediating the energy transfer from the metal oxide to the graphite oxide. Multidimensional time resolved spectroscopy further describes the effect of the carbon phase on the energy transfer pathways in the material.


Synthesis Of Novel Aporphine-Inspired Neuroreceptor Ligands, Nirav R. Kapadia Feb 2016

Synthesis Of Novel Aporphine-Inspired Neuroreceptor Ligands, Nirav R. Kapadia

All Dissertations, Theses, and Capstone Projects

Aporphines are a group of tetracyclic alkaloids that belong to the ubiquitous tetrahydroisoquinoline family. The aporphine template is known to be associated with a range of biological activities. Aporphines have been explored as antioxidants, anti-tuberculosis, antimicrobial and anticancer agents. Within the Central Nervous Systems (CNS), aporphine alkaloids are known to possess high affinity for several clinically valuable targets including dopamine receptors (predominantly D1 and D2), serotonin receptors (5-HT1A and 5-HT7) and α adrenergic receptors. Aporphines are also inhibitors of the acetylcholinesterase enzyme – a clinical target for the treatment of Alzheimer’s disease. Considering the diverse profile ...


Accessing Medicinally-Relevant Scaffolds Via Organocatalyzed Cascade Reactions, Joshua Hadley Jones Sep 2015

Accessing Medicinally-Relevant Scaffolds Via Organocatalyzed Cascade Reactions, Joshua Hadley Jones

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The field of asymmetric catalysis embodies the efforts of chemists to mimic the stereoselectivity routinely achieved by biological systems. Asymmetric organocatalysis, a sub-field of asymmetric catalysis, is broadly based on the catalytic activity of non-transition metal, small molecules that transmit chirality to substrates. This dissertation describes experimental work towards the construction of versatile, medicinally-relevant molecular scaffolds using chiral, diarylprolinol silyl ether organocatalysts. Specifically, these catalysts were used in 1-pot, iminium-enamine catalyzed cascade reactions to functionalize α,β-unsaturated aldehydes. A comprehensive review of iminium and enamine organocatalysis is provided, including its development towards iminium-enamine cascade reactions. This review provides background for ...


Studies Toward A General Synthesis Of Poly-Substituted Alpha-Hydroxytropolones, Christine Marie Meck Sep 2015

Studies Toward A General Synthesis Of Poly-Substituted Alpha-Hydroxytropolones, Christine Marie Meck

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Chapter 1: This chapter gives a brief history of α-hydroxytropolones, how they were discovered and unique properties of these substrates. Included is a background on the bioactivity of these substrates in cellular targets such as bacteria, fungi, parasites, tumors and toxicity, as well as their ability to inhibit various metallo-based enzymes. Structure activity relationships studies are reviewed on important metalloenzymes HIV-Reverse Transcriptase (RT) and Inositol monophosphatase (IMPase). Finally the chapter finishes with a synthetic overview of α-hydroxytropolones including natural product targets such as puberulic acid, puberulonic acid, β-thujaplicinol, and β-hydroxytropolone.

Chapter 2: A brief review on β-hydroxy-γ-pyrone based oxidopyrylium cycloadditions ...


Towards The Total Synthesis Of (+/-)-Gephyrotoxin 287c, Maciej E. Domaradzki Feb 2015

Towards The Total Synthesis Of (+/-)-Gephyrotoxin 287c, Maciej E. Domaradzki

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Studies directed toward the total synthesis of (+/-)-Gephyrotoxin 287C are described herein. Even though the target alkaloid has been synthesized four times to date, it still presents an interesting synthetic challenge. Our ultimate goal is to develop an efficient enantioselective synthetic route utilizing oxazolone chemistry in order to demonstrate its utility as a dienophilic component in intramolecular Diels-Alder reactions. This is part of a greater ongoing study aimed at a range of suitable alkaloid targets.

Chapter 1 provides introduction to frog toxins as secondary metabolites and subsequently shifts to the target alkaloid. (+/-)-Gephyrotoxin 287C was originally described by Daly and ...


Development Of Cell-Active Inhibitors And Activity-Based Probe Of Cysteine Cathepsins, Dibyendu Dana Oct 2014

Development Of Cell-Active Inhibitors And Activity-Based Probe Of Cysteine Cathepsins, Dibyendu Dana

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Cysteine cathepsins are an important class of enzymes that coordinate a variety of important cellular processes, and are implicated in various types of human diseases. Still however, many of their cellular function remain poorly understood. Chemical biology approaches employing small molecules can be utilized for this purpose. Unfortunately small molecule probes that are cell-permeable and non-peptidyl in nature are scarcely available.

In this work, first a library of sulfonyloxiranes is synthesized. From this library, 2-(2-ethylphenylsulfonyl)oxirane is identified as a selective inhibitor of cysteine cathepsins. Cell-based study reveals that 2-(2-ethylphenylsulfonyl)oxirane is a cell-permeable, covalent, and irreversible inhibitor ...


Synthesis Of Biologically Important C-Glycosides From Simple C-Glycosyl Alkenes, Ahmad Sabri Altiti Oct 2014

Synthesis Of Biologically Important C-Glycosides From Simple C-Glycosyl Alkenes, Ahmad Sabri Altiti

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C-Glycosides are carbohydrate analogues in which the glycosidic oxygen is replaced with a methylene substituent. Because of their stability under acidic hydrolysis or enzymatic cleavage, they are widely used as mimetics of their parent O-glycosides in medicinal chemistry. This thesis describes the development of new synthetic methods for C-glycosides, which center on the use of readily available, simple C-allyl glycosides as precursors. C- glycosides of three structurally distinct and pharmacologically interesting carbohydrates, the immunostimulatory glycolipid C-KRN700, the insulin mimetic glycoinositol β-galactosamine-(1→4)-3-O-methyl-D-chiro-inositiol (INS-2), and α-mannose-(1→6)-D-myo-inositiol, a subunit of the cell wall in Mycobacterium tuberculosis, will ...


Carbon And Nitrogen Dynamics From Slow Pools Of Soil Organic Matter In A Temperate Forest: Pyrogenic Organic Matter And And Root Litter, Fernanda Dos Santos Oct 2014

Carbon And Nitrogen Dynamics From Slow Pools Of Soil Organic Matter In A Temperate Forest: Pyrogenic Organic Matter And And Root Litter, Fernanda Dos Santos

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Soil organic matter (SOM) is the dominant reservoir of organic carbon (OC) in terrestrial ecosystems, storing approximately three times the size of the C pool in the atmosphere. In temperate forests, a major fraction of the SOM consists of slowly decaying soil organic C (SOC) pools. While slowly cycling C pools constitute a large reservoir of stable C in soils, the dominant environmental factors controlling this C pool remain unresolved. This research investigates two significant, but poorly characterized slowly decaying C pools: fine root litter (< 2mm) and thermally altered plant biomass (pyrogenic organic matter, PyOM). Specifically, I used compound-specific stable isotope analysis (13C and 15N) as my main methodological approach to examine the (1) decomposition ...


Oxocarbenium Ion And Alkene Metathesis Strategies For The Synthesis Of Complex Cyclohexanes, Clayton Errol Mattis Oct 2014

Oxocarbenium Ion And Alkene Metathesis Strategies For The Synthesis Of Complex Cyclohexanes, Clayton Errol Mattis

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Highly oxygenated cyclohexanes comprise the structures of a number of pharmacologically interesting molecules, including potently bioactive natural products and carbapyranosides. The latter, which are unnatural analogues of carbohydrates in which the ring oxygen of the parent sugar is replaced with a methylene group, have attracted interest as hydrolytically stable mimetics of their parent O-glycosides. This research reports the development of two general methodologies for the synthesis of highly oxygenated cyclohexanes: (1) Oxocarbenium Ion Cyclization (OCC) and (2) Ring Closing Metathasis (RCM).

Chapter one gives a review of the literature on the synthesis for highly oxygenated cyclohexanes.

Previous results from this ...


Nickel-Catalyzed Cross-Coupling Reactions Involving Secondary And Tertiary Alkyl Nucleophiles, Amruta Ajit Joshi Feb 2014

Nickel-Catalyzed Cross-Coupling Reactions Involving Secondary And Tertiary Alkyl Nucleophiles, Amruta Ajit Joshi

All Dissertations, Theses, and Capstone Projects

In the first chapter, introduction of transition metal-catalyzed cross-coupling reactions has been given. These transition metal-catalyzed C-C bond forming reactions have been used extensively in organic synthesis. Among them, C(sp2)-C(sp2) bond forming reactions have been widely studied over decades. More recently, some reports have demonstrated the use of C(sp3) nucleophiles and electrophiles in cross-coupling reactions. However, use of secondary and tertiary alkyl nucleophiles has remained a challenge due to competitive β-hydride elimination and slow transmetallation of bulky secondary and tertiary alkyl organometallic nucleophiles.

In the second chapter, the first general nickel-catalyzed Negishi reaction for the cross-coupling ...