Developing Novel Synthetic Methodologies Using Hypervalent
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BI(III) Initiated Cyclization Reactions and Iodonium Fragmentation Kinetics
W&M ScholarWorks Dissertations, Theses, and Masters Projects Theses, Dissertations, & Master Projects 2005 BI(III) Initiated Cyclization Reactions and Iodonium Fragmentation Kinetics Yajing Lian College of William & Mary - Arts & Sciences Follow this and additional works at: https://scholarworks.wm.edu/etd Part of the Inorganic Chemistry Commons Recommended Citation Lian, Yajing, "BI(III) Initiated Cyclization Reactions and Iodonium Fragmentation Kinetics" (2005). Dissertations, Theses, and Masters Projects. Paper 1539626842. https://dx.doi.org/doi:10.21220/s2-zj7g-fp23 This Thesis is brought to you for free and open access by the Theses, Dissertations, & Master Projects at W&M ScholarWorks. It has been accepted for inclusion in Dissertations, Theses, and Masters Projects by an authorized administrator of W&M ScholarWorks. For more information, please contact [email protected]. BI(III) INITIATED CYCLIZATION REACTIONS AND IODONIUM FRAGMENTATION KINETICS A Thesis Presented to The Faculty of the Department of Chemistry The College of William and Mary in Virginia In Partial Fulfillment Of the Requirements for the Degree of Master of Science by Yajing Lian 2005 APPROVAL SHEET This thesis is submitted in partial fulfillment of The requirements for the degree of Master of Science A Yajing Lian Approved by the Committee, December 20, 2005 Robert J. Hinkle, Chair Christopher Jl A] Robert D. Pike TABLE OF CONTENTS Page Acknowledgements VI List of Tables Vll List of Schemes V lll List of Figures IX Abstract XI Introduction Chapter I Secondary -
Chapter 1 Tropone and Tropolone
School of Molecular and Life Sciences New Routes to Troponoid Natural Products Jason Matthew Wells This thesis is presented for the Degree of Doctor of Philosophy of Curtin University November 2018 Declaration To the best of my knowledge and belief this thesis contains no material previously pub- lished by any other person except where due acknowledgement has been made. This thesis contains no material which has been accepted for the award of any other degree or diploma in any other university. Signature: Date: i Abstract Malaria is an infectious disease found in humans and other animals, it is caused by a single-cell parasite of the Plasmodium genus with many different substrains. Of these, P. falciparum is the most deadly to humans causing the majority of deaths. Although research into the area of antimalarial compounds is wide spread, few have been devel- oped with new structural features. Cordytropolone 37 is a natural product isolated in 2001 from the insect pathogenic fungus Cordyceps sp. BCC 1681 and has been shown to have antimalarial activity against P. falciparum. It has a structure unrelated to antimalarial com- pounds currently used in therapy. It does not contain a peroxide bridge as with artemisinin 25 or quinoline rings as with chloroquine 22. This unique structure indicates that it could possibly interact with the malaria parasite in a fashion unlike current treatments. In order for cordytropolone to be further developed as a potential treatment, it must first be synthe- sised in a laboratory environment. This study attempts to develop the first total synthesis of cordytropolone. H HO O N O O N O N H H H O O Cl HO O 22 25 37 Figure 0.0.1: Cordytropolone 37 has a unique structure compared to the current common malaria treatments The first method investigated towards the total synthesis of cordytropolone involved an intramolecular Buchner ring expansion. -
Design, Synthesis and Applications of Novel Hypervalent Iodine Reagents
Design, Synthesis and Applications of Novel Hypervalent Iodine Reagents A Thesis Submitted to Cardiff University in Fulfilment of the Requirements for the Degree of Doctor of Philosophy by Jihan Qurban PhD Thesis July 2019 Cardiff University Jihan Qurban PhD Thesis 2019 __________________________________________________________________________________ DECLARATION This work has not been submitted in substance for any other degree or award at this or any other university or place of learning, nor is being submitted concurrently in candidature for any degree or other award. Signed …………………………… (Jihan Qurban) Date ………………….… STATEMENT 1 This thesis is being submitted in partial fulfillment of the requirements for the degree of ……………………… (insert MCh, MD, MPhil, PhD etc, as appropriate) Signed …………………………… (Jihan Qurban) Date ………………….… STATEMENT 2 This thesis is the result of my own independent work/investigation, except where otherwise stated, and the thesis has not been edited by a third party beyond what is permitted by Cardiff University’s Policy on the Use of Third-Party Editors by Research Degree Students. Other sources are acknowledged by explicit references. The views expressed are my own. Signed …………………………… (Jihan Qurban) Date ………………….… STATEMENT 3 I hereby give consent for my thesis, if accepted, to be available online in the University’s Open Access repository and for inter-library loan, and for the title and summary to be made available to outside organisations. Signed …………………………… (Jihan Qurban) Date ………………….… STATEMENT 4: PREVIOUSLY APPROVED BAR ON ACCESS I hereby give consent for my thesis, if accepted, to be available online in the University’s Open Access repository and for inter-library loans after expiry of a bar on access previously approved by the Academic Standards & Quality Committee. -
A Metal-Free Approach to Biaryl Compounds: Carbon-Carbon Bond Formation from Diaryliodonium Salts and Aryl Triolborates
Portland State University PDXScholar Dissertations and Theses Dissertations and Theses Winter 4-3-2015 A Metal-Free Approach to Biaryl Compounds: Carbon-Carbon Bond Formation from Diaryliodonium Salts and Aryl Triolborates Kuruppu Lilanthi Jayatissa Portland State University Follow this and additional works at: https://pdxscholar.library.pdx.edu/open_access_etds Part of the Catalysis and Reaction Engineering Commons Let us know how access to this document benefits ou.y Recommended Citation Jayatissa, Kuruppu Lilanthi, "A Metal-Free Approach to Biaryl Compounds: Carbon-Carbon Bond Formation from Diaryliodonium Salts and Aryl Triolborates" (2015). Dissertations and Theses. Paper 2229. https://doi.org/10.15760/etd.2226 This Thesis is brought to you for free and open access. It has been accepted for inclusion in Dissertations and Theses by an authorized administrator of PDXScholar. Please contact us if we can make this document more accessible: [email protected]. A Metal-Free Approach to Biaryl Compounds: Carbon-Carbon Bond Formation from Diaryliodonium Salts and Aryl Triolborates. by Kuruppu Lilanthi Jayatissa A thesis submitted in partial fulfillment of the requirement for the degree of Master of Science in Chemistry Thesis Committee: David Stuart, Chair Robert Strongin Theresa McCormick Portland State University 2015 Abstract Biaryl moieties are important structural motifs in many industries, including pharmaceutical, agrochemical, energy and technology. The development of novel and efficient methods to synthesize these carbon-carbon bonds is at the forefront of synthetic methodology. Since Ullmann’s first report of stoichiometric Cu-mediated homo-coupling of aryl halides, there has been a dramatic evolution in transition metal catalyzed biaryl cross-coupling reactions. -
Metathetical Redox Reaction of (Diacetoxyiodo)Arenes and Iodoarenes
Article Metathetical Redox Reaction of (Diacetoxyiodo)arenes and Iodoarenes Antoine Jobin-Des Lauriers and Claude Y. Legault * Received: 25 November 2015 ; Accepted: 15 December 2015 ; Published: 17 December 2015 Academic Editors: Wesley Moran and Arantxa Rodríguez Centre in Green Chemistry and Catalysis, Department of Chemistry, University of Sherbrooke, 2500 boul. de l’Université, Sherbrooke, QC J1K 2R1, Canada; [email protected] * Correspondence: [email protected]; Tel./Fax: +1-819-821-8017 Abstract: The oxidation of iodoarenes is central to the field of hypervalent iodine chemistry. It was found that the metathetical redox reaction between (diacetoxyiodo)arenes and iodoarenes is possible in the presence of a catalytic amount of Lewis acid. This discovery opens a new strategy to access (diacetoxyiodo)arenes. A computational study is provided to rationalize the results observed. Keywords: hypervalent iodine; (diacetoxyiodo)arenes; metathesis 1. Introduction In the recent years, the development of hypervalent iodine-mediated synthetic transformations has been receiving growing attention [1–5]. This is not surprising considering the importance of improving oxidative reactions and reducing their environmental impact. Hypervalent iodine reagents are a great alternative to toxic heavy metals often used to effect similar transformations [6–10]. Among the plethora of iodine(III) compounds [11], it is undeniable that the (diacetoxyiodo)arenes remain the most common and used ones [12]. They are usually stable solids and can serve as precursors to numerous other iodanes, such as other (diacyloxyiodo)arenes and [hydroxy(tosyloxy) iodo]arenes [13,14]. Access to (diacetoxyiodo)arenes is, of course, usually accomplished by the oxidation of the corresponding iodoarene substrate. -
SELECTIVE C–H and ALKENE FUNCTIONALIZATION VIA ORGANIC PHOTOREDOX CATALYSIS Nicholas Paul Ralph Onuska a Dissertation Submitte
SELECTIVE C–H AND ALKENE FUNCTIONALIZATION VIA ORGANIC PHOTOREDOX CATALYSIS Nicholas Paul Ralph Onuska A dissertation submitted to the faculty at the University of North Carolina at Chapel Hill in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry Chapel Hill 2021 Approved by: David Nicewicz Erik Alexanian Jeffrey Aubé Alexander Miller Andrew Moran © 2021 Nicholas Paul Ralph Onuska ALL RIGHTS RESERVED ii ABSTRACT Nicholas Paul Ralph Onuska: Selective C–H and Alkene Functionalization Via Organic Photoredox Catalysis (Under the direction of David A. Nicewicz) Photoinduced electron transfer (PET) can be defined as the promotion of an electron transfer reaction through absorption of a photon by a reactive species in solution. Photoredox catalysis has leveraged previous knowledge of PET processes to enable a wide variety of high value chemical transformations. Most early work in the field of photoredox catalysis centered around the use of visible-light absorbing transition metal catalyst systems based on ruthenium or iridium polypyridyl scaffolds, organic redox chromophores offer a more sustainable, accessible, and versatile alternative to these complexes. Organic photoredox catalysts are often less expensive, easier to prepare, and have expanded redox windows relative to many known transition-metal photoredox catalysts, enabling the generation of a wider variety of single electron reduced/oxidized species. This ultimately translates into the development of previously undiscovered modes of reactivity. Herein is described the development and mechanistic study of a several C–H and alkene functionalization reactions facilitated by visible light-absorbing acridinium salts, as well as the discovery and characterization of a neutral organic radical which possess one of the most negative excited state oxidation potentials observed to date. -
Chapter 9 Hydrogen
Chapter 9 Hydrogen Diborane, B2 H6• is the simplest member of a large class of compounds, the electron-deficient boron hydrid Like all boron hydrides, it has a positive standard free energy of formation, and so cannot be prepared direct from boron and hydrogen. The bridge B-H bonds are longer and weaker than the tenninal B-H bonds (13: vs. 1.19 A). 89.1 Reactions of hydrogen compounds? (a) Ca(s) + H2Cg) ~ CaH2Cs). This is the reaction of an active s-me: with hydrogen, which is the way that saline metal hydrides are prepared. (b) NH3(g) + BF)(g) ~ H)N-BF)(g). This is the reaction of a Lewis base and a Lewis acid. The product I Lewis acid-base complex. (c) LiOH(s) + H2(g) ~ NR. Although dihydrogen can behave as an oxidant (e.g., with Li to form LiH) or reductant (e.g., with O2 to form H20), it does not behave as a Br0nsted or Lewis acid or base. It does not r with strong bases, like LiOH, or with strong acids. 89.2 A procedure for making Et3MeSn? A possible procedure is as follows: ~ 2Et)SnH + 2Na 2Na+Et3Sn- + H2 Ja'Et3Sn- + CH3Br ~ Et3MeSn + NaBr 9.1 Where does Hydrogen fit in the periodic chart? (a) Hydrogen in group 1? Hydrogen has one vale electron like the group 1 metals and is stable as W, especially in aqueous media. The other group 1 m have one valence electron and are quite stable as ~ cations in solution and in the solid state as simple 1 salts. -
Enantioselective Iodine(I/III) Catalysis in Organic Synthesis, Which Has Been Published in Final Form At
"This is the peer reviewed version of the following article: Enantioselective Iodine(I/III) Catalysis in Organic Synthesis, which has been published in final form at https://doi.org/10.1002/adsc.201800521 . This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving http://olabout.wiley.com/WileyCDA/Section/id-820227.html “ Enantioselective Iodine(I/III) Catalysis in Organic Synthesis Andrea Flores,a Eric Cots,a Julien Bergès,a and Kilian Muñiza,b* a Institute for Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science, Av. Països Catalans 16, 43007 Tarragona, Spain Fax: +34 977 920 224. E-mail: [email protected] b ICEA Passeig Lluís Companys, 23, 08010 Barcelona, Spain Abstract. Chiral aryliodine(III) reagents have provided an advanced concept for enantioselective synthesis and catalysis. Keywords: Chirality; Enantioselective Synthesis; With the advent of chiral iodine(I/III) catalysis, a large Homogeneous Catalysis; Iodine; Oxidation number of different structures have been explored in the area. The currently most prominent catalyst design is based on a resorcinol core and the attachment of two lactic side chains bearing ester or amide groups. It enables a privileged modular catalyst synthesis, in which fine-tuning with respect to the specific reaction requirement is straightforward. The present overview summarizes the structural variation and optimization of such chiral aryliodine catalysts and discusses structural properties of the active iodine(III) catalyst states. The status quo of enantioselective iodine(I/III) oxidation catalysis with respect to intramolecular and intermolecular reaction control is reviewed, and specific aspects of the individual catalytic cycles are discussed. -
Towards the Synthesis of Isocoronene
Department of Chemistry Towards the Synthesis of Isocoronene Iain William Currie This thesis is presented for the Degree of Doctor of Philosophy of Curtin University April 2018 Declaration To the best of my knowledge and belief this thesis contains no material previously published by any other person except where due acknowledgement has been made. This thesis contains no material which has been accepted for the award of any other degree or diploma in any other university. Signature: Date: i Abstract The concept of aromaticity and its implications are fundamentally important to a wide range of applied sciences involving organic molecules. Aromaticity arises from the delocalisation of electrons through a cyclic conjugated system known as a conjugated circuit. Monocyclic aromatic compounds possess a single conjugated circuit while polycyclic aromatic hydrocarbons (PAHs) may have numerous potential conjugated circuits. The aromaticity of PAHs is complicated by the presence of multiple conjugated circuits which may have varying contribution to the overall properties depending on several factors such as geometry and topology. Isocoronene 105 is one example of a PAH classified as a non-benzenoid corannulene. Isocoronene is unique among corannulenes since the conjugated circuits are restricted to the peripheral and central rings only. Isocoronene has been used as a model compound for computational studies into aromaticity and may provide the first example of a superaromatic molecule. The synthesis of novel aromatic structures such as isocoronene is essential in providing unambiguous empirical data which can be used to verify and develop computational methods. In addition, the development of new synthetic methodologies towards PAHs is important in the field of organic electronics. -
Decomposition of Ruthenium Olefin Metathesis Catalyst
catalysts Review Decomposition of Ruthenium OlefinOlefin Metathesis CatalystMetathesis Catalyst Magdalena Jawiczuk 1,, Anna Anna Marczyk Marczyk 1,21,2 andand Bartosz Bartosz Trzaskowski Trzaskowski 1,* 1,* 1 1 CentreCentre of of New New Technologies, Technologies, University University of of Warsaw, Warsaw, Banacha Banacha 2c, 2c, 02-097 02-097 Warsaw, Warsaw, Poland; [email protected]@cent.uw.edu.pl (M.J.); (M.J.); [email protected] [email protected] (A.M.) (A.M.) 2 Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland 2 Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland * Correspondence: [email protected] * Correspondence: [email protected] Received: 28 28 June 2020; Accepted: 02 2 AugustAugust 2020;2020; Published:Published: 5date August 2020 Abstract: RutheniumRuthenium olefin olefin metathesis metathesis catalysts catalysts are are one one of of the most commonly used class of catalysts. There There are are multiple multiple reviews reviews on on their their us useses in in various branches of chemistry and other sciences but a detailed review of their decomposition is missing, despite a large number of recent and important advances advances in in this this field. field. In In particular, particular, in in the the last last five five years years several several new new mechanism mechanism of decomposition,of decomposition, both both olefin-driven olefin-driven as well as well as induc as induceded by external by external agents, agents, have have been been suggested suggested and usedand usedto explain to explain differences differences in the decomposition in the decomposition rates and rates the metathesis and the metathesis activities activitiesof both standard, of both N-heterocyclicstandard, N-heterocyclic carbene-based carbene-based systems and systems the recently and the developed recently developed cyclic alkyl cyclic amino alkyl carbene- amino containingcarbene-containing complexes. -
Methodology Studies on One and Two Carbon Ring Expansion on Polyether Polycyclic Natural Products
Mamalis, Dimitrios (2020) Methodology studies on one and two carbon ring expansion on polyether polycyclic natural products. MRes thesis. http://theses.gla.ac.uk/81800/ Copyright and moral rights for this work are retained by the author A copy can be downloaded for personal non-commercial research or study, without prior permission or charge This work cannot be reproduced or quoted extensively from without first obtaining permission in writing from the author The content must not be changed in any way or sold commercially in any format or medium without the formal permission of the author When referring to this work, full bibliographic details including the author, title, awarding institution and date of the thesis must be given Enlighten: Theses https://theses.gla.ac.uk/ [email protected] Methodology Studies on One and Two Carbon Ring Expansion on Polyether Polycyclic Natural Products Dimitrios Mamalis, BSc Chemistry Thesis Submitted in the fulfillment of the requirements for the degree of Master in Research School of Chemistry College of Science and Engineering University of Glasgow September 2020 Abstract Medium sized cyclic ethers are found in many natural products, with the most notable example being the polyether polycyclic family of marine toxins. Due to their increased size loss of entropy, torsional strain and unfavourable transannular interactions, as well as other effects require different synthetic approaches than the smaller homologues. In this work, different pathways were explored for the efficient synthesis of the seven-, eight- and nine- membered rings of marine polyether polycyclic natural products, through the expansion of a common six-membered ether substrate. -
Thesis Yahui Wang
GOLD CARBENES FROM CYCLOHEPTATRIENES: GENERATION AND FATE. Yahui Wang Dipòsit Legal: T 1612-2015 ADVERTIMENT. L'accés als continguts d'aquesta tesi doctoral i la seva utilització ha de respectar els drets de la persona autora. Pot ser utilitzada per a consulta o estudi personal, així com en activitats o materials d'investigació i docència en els termes establerts a l'art. 32 del Text Refós de la Llei de Propietat Intel·lectual (RDL 1/1996). Per altres utilitzacions es requereix l'autorització prèvia i expressa de la persona autora. En qualsevol cas, en la utilització dels seus continguts caldrà indicar de forma clara el nom i cognoms de la persona autora i el títol de la tesi doctoral. No s'autoritza la seva reproducció o altres formes d'explotació efectuades amb finalitats de lucre ni la seva comunicació pública des d'un lloc aliè al servei TDX. Tampoc s'autoritza la presentació del seu contingut en una finestra o marc aliè a TDX (framing). Aquesta reserva de drets afecta tant als continguts de la tesi com als seus resums i índexs. ADVERTENCIA. El acceso a los contenidos de esta tesis doctoral y su utilización debe respetar los derechos de la persona autora. Puede ser utilizada para consulta o estudio personal, así como en actividades o materiales de investigación y docencia en los términos establecidos en el art. 32 del Texto Refundido de la Ley de Propiedad Intelectual (RDL 1/1996). Para otros usos se requiere la autorización previa y expresa de la persona autora. En cualquier caso, en la utilización de sus contenidos se deberá indicar de forma clara el nombre y apellidos de la persona autora y el título de la tesis doctoral.