Synthesis, Characterization, and Theranostic Applications of Pyridine Containing Macrocyclic Ligands and Their Divalent Transition Metal Complexes

Synthesis, Characterization, and Theranostic Applications of Pyridine Containing Macrocyclic Ligands and Their Divalent Transition Metal Complexes PDF Author: Kristof Pota
Publisher:
ISBN:
Category : Ligands (Biochemistry)
Languages : en
Pages : 0

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Synthesis and Characterization of Transitional Metal Pyridine Containing Complexes with Both Catalytic and Therapeutic Applications

Synthesis and Characterization of Transitional Metal Pyridine Containing Complexes with Both Catalytic and Therapeutic Applications PDF Author: Magy Amir Maurice Mekhail
Publisher:
ISBN:
Category : Cyclophanes
Languages : en
Pages : 0

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Book Description
Pyridinophanes derived from pyclen are the focus of many studies as biological mimics, chelators, and catalytic precursors. Therefore, the desire to tune the reactivity of metal pyridinophane complexes has inspired modifications that include expansion of ring size and substitutions to the N-atoms. However, substitution on the pyridine moiety is largely unexplored to date. Herein, new synthetic strategies for pyclen-congeners bearing electron donating and electron withdrawing groups are introduced, resulting in doubling the number of pyridine functionalized molecules in literature. Further, the influence of such modifications on properties and reactivity of two metals (Fe(III) and Cu(II)) is described. For the Fe(III) system, 4-substitution of the pyridine ring successfully provides a regulatory handle on the electronic properties and the catalytic C-C coupling activity of the respective Fe complexes. These are the first examples of a structure-activity relationship study with the impact of electronic properties decoupled from structural properties and investigated. The Fe(III) system was also explored in a catalase mimetic study to determine the role of ligand design on the activity of the metal center through changing electronic properties and rigidity of the ligand. Varying the electronic properties of the ligand has a minor effect on catalase activity, but changes to the geometry of the complex have significant impacts on the system. This activity was also successfully observed to cellular models. The Cu(II) system was investigated as a superoxide dismutase mimic. Cu(II) Pyclen complexes, specifically, has been shown to match its coordination environment and to have high binding affinity. My studies highlight that modifications to the pyridine ring of the ligand can tune the redox potential, while exhibiting high binding stabilities and retaining the coordination environment. In fact, one of the complexes studied exhibits one of the highest SOD activities reported to date, which is hypothesized to be the result of not only the electronic properties of the Cu center but also the high binding stability exhibited by this complex. Altogether, this work focused on functionalizing the pyridine ring in pyridinophanes and studying the effect of the modifications on the electronics of metal complexes and their reactivity with both catalytic and potential therapeutic application.

Synthesis, Characterization, and Applications of Pyridine- and Pyridol-based Azamacrocyclic Transition Metal Complexes

Synthesis, Characterization, and Applications of Pyridine- and Pyridol-based Azamacrocyclic Transition Metal Complexes PDF Author: Hannah May Johnston
Publisher:
ISBN:
Category : Macrocyclic compounds
Languages : en
Pages : 298

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Recent Developments in the Synthesis and Applications of Pyridines

Recent Developments in the Synthesis and Applications of Pyridines PDF Author: Parvesh Singh
Publisher: Elsevier
ISBN: 0323914594
Category : Science
Languages : en
Pages : 650

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Book Description
Recent Developments in the Synthesis and Applications of Pyridines is a comprehensive handbook for organic chemists working on innovative approaches to the synthesis of pyridines. Written by scientists in both academia and industry and designed to be a standalone reference, the book features reviews, research results and case studies on synthetic methods and applications of pyridine-based chemotypes. The book will bridge the gap between industry and academia by presenting recent innovative approaches to the synthesis of pyridines, diverse application of pyridines in drug development, heterogeneous catalysis and material science, as well as benchtop to shelf narratives of pyridine-based compounds in the industry. The role of computational chemistry in the development of pyridine-based bioactive molecules is also included. This reference is essential for researchers in organic chemistry both in academic and industrial settings, postgraduates in chemistry and medicinal chemistry. - Includes a detailed review of recent research on the reactivity, synthesis and applications of pyridines - Features concise accounts of the reactivity, synthetic and optimized protocols - Discusses the medicinal, inorganic and polymer chemistry applications of pyridines

Chiral Iron Pyridine Complexes and Ruthenium Complexes with N-Heterocyclic Carbene and Macrocyclic (N, O) Donor Atom Ligands

Chiral Iron Pyridine Complexes and Ruthenium Complexes with N-Heterocyclic Carbene and Macrocyclic (N, O) Donor Atom Ligands PDF Author: Kar-Yee Lam
Publisher:
ISBN: 9781361034422
Category :
Languages : en
Pages :

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This dissertation, "Chiral Iron Pyridine Complexes and Ruthenium Complexes With N-heterocyclic Carbene and Macrocyclic (N, O) Donor Atom Ligands: Synthesis, Catalytic Activity and Biological Studies" by Kar-yee, Lam, 林嘉儀, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled CHIRAL IRON PYRIDINE COMPLEXES AND RUTHENIUM COMPLEXES WITH N-HETEROCYCLIC CARBENE AND MACROCYCLIC(N, O) DONOR ATOM LIGANDS: SYNTHESIS, CATALYTIC ACTIVITY AND BIOLOGICAL STUDIES Submitted by Lam Kar Yee For the degree of Doctor of Philosophy at The University of Hong Kong in April 2016 Transition metal complexes are widely applied as catalysts for organic transformation reactions such as the oxygen atom and nitrene transfer reactions and there is a growing interest to develop the medicinal applications of transition metal complexes. The studies of reactive metal-oxo and metal-nitrene intermediates are important in probing the underlying reaction mechanisms. This thesis is comprised of three main parts. In the first part, iron complexes with chiral pyridine ligands, such as 4′,6-disubstituted 2,2′ 6′,2″-terpyridine (NNN ) and 4′,6,6″-trisubstituted 2,2′ 6′,2″''-terpyridine (NNN ), were studied for their catalytic activities in asymmetric epoxidation, aziridination, amidation and sulfimidation reactions. The Fe-NNN complex catalyzed intermolecular nitrene transfer/CN bond formation reactions of styrenes with PhINTs in moderate product yields. For the asymmetric intramolecular amidation, the Fe-NNN complex can catalyze intramolecular C-N bond formation using PhI(OAc) as oxidant to form five- or six-membered ring products. The highest product yield obtained was 91 %. The complete conversion of para-substituted phenyl methyl sulfides to corresponding sulfimides was observed by using the Fe-NNN 1 2 complex as catalyst. Both the Fe-NNN and Fe-NNN complexes catalyzed asymmetric epoxidation of styrene using PhIO as oxidant at 0 C. The reaction intermediates of the nitrene/oxygen transfer reactions were studied by ESI-MS and high-valent iron-ligand multiple bonded species are proposed to be the reaction intermediates. In the second part, ruthenium pincer N-heterocyclic carbene (CNC) complexes were prepared and characterized by spectroscopic means and X-ray crystallography. II 2+ Complex [Ru (CNC)(bpy)(MeCN)], in which the CNC ligand adopts a fac-coordination mode and contains reactive CH bond of bridging methylene group, was found to react with PhINTs to result in the formation of a new CN bond and cleavage of one existing NC(methylene) bond of the CNC ligand, as revealed by X-ray crystal structure determination of the ruthenium complex product. The reaction 2+ of [Ru(CNC)(bpy)(MeCN)] with PhINTs was monitored by ESI-MS, UV-vis, and NMR spectroscopy; a paramagnetic Ru(III)-amido complex was isolated, which apparently resulted from intramolecular imido/nitrene CH insertion of a Ru(IV)-imido/nitrene intermediate and was found to undergo the observed CN bond cleavage. Such type of CN bond cleavage induced by metal-mediated imido/nitrene insertion is unprecedented in literature. The final part of this thesis is the study of the anti-angiogenic and anti-metastatic properties of the ruthenium complexes. Ruthenium complexes with different oxidation states (+2 and +3) and ligands (pincer NHC and macrocyclic (N, O) donor atom ligands) were examined for their cytotoxicity and anti-angiogenesis activity. III Among the complexes studied, [Ru (N O )Cl ]Cl (Ru-1) displays promising 2 2 2 inhibi

Exploring Chemistry with Pyridine Derivatives

Exploring Chemistry with Pyridine Derivatives PDF Author: Satyanarayan Pal
Publisher: BoD – Books on Demand
ISBN: 1803566620
Category : Science
Languages : en
Pages : 251

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Book Description
This book discusses the chemistry and applications of pyridine derivatives. The library of pyridine derivatives is growing steadily with numerous synthetic analogues already described and the identification of new, naturally occurring pyridine-based compounds. The book includes ten chapters organized into two parts. The first part focuses on the numerous types of reactions that arise from pyridine derivatives. The second part examines the pharmaceutical applications of pyridine derivatives as well as their usefulness as sensors for metal cations and extracting agents for platinum group metals.

Rational Design, Synthesis and Characterization of Amide Functionalized Pyridine and Benzimidazole Transition Metal Complexes

Rational Design, Synthesis and Characterization of Amide Functionalized Pyridine and Benzimidazole Transition Metal Complexes PDF Author: Samuel S. K. Asem
Publisher:
ISBN:
Category : Benzimidazoles
Languages : en
Pages : 576

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Book Description
This study expands our efforts to make a new class of Pt (II) compounds analogous to cisplatin and its derivatives using sterically hindered ligands. Pt compounds in this series have been synthesized using specially designed pyridine and benzimidazole ligands. These heterocycles, amide functionalized at position 2 with aryl and alkyl pendants, rapidly change their mode of coordination depending on the pH of the medium. These ligands, synthesized using condensation chemistry, also coordinate to Co(II), Ni(H), Cu(lI), and Zn(1I) generally as anionic bis-chelates through the benzimidazole nitrogen and the carbonyl oxygen, creating a four-coordinate complex with the exception of an unusual trigonal bipyramidal Zn(H) complex. I H NMR temperature studies reveal that these ligands interconvert between imide and amide isomers and that electron withdrawing pendants favor amide isomers. Crystal structures of Co(II) and Ni(1I) complexes of N-( I-methylbenzimidazol-2-yl)cyclohexanecarboxamide, for example, show two ligands bind per metal ion when reacted with acetate and nitrate salts. The bischelates of these Ni(1I) complexes also show expansions of their coordination spheres from four to five-coordinate. Furthermore, these Ni(II) bis-chelated complexes possess square planar or distorted 4-coordinate geometries. The synthesis and properties of several new Pt (II) complexes containing these ligands will be presented. A second generation and novel complex class containing metal-binding, linker and recognition domains is reported. Both classes of Pt complexes were obtained using a synthetic methodology which favors the cis isomers. The second generation complex crystallizes in the monoclinic space group P2dn with lattice dimensions a = 17.7393(5) A, b = 11.4632(3) A, c = 19.3959(5) A and ~ = 99.794(3)°. These complexes have been characterized using physical methods that include X-ray crystallography, IH &13C NMR, Mass spectrometry, UV and IR spectroscopies. Complexes similar in structure to cisplatin and carboplatin show varying cytotoxic properties toward different cancer cell lines. Additionally, some of these new Pt complexes show comparable and promising cytotoxicity against prostate cancer cell lines.

Transition Metal-Catalyzed Pyridine Synthesis

Transition Metal-Catalyzed Pyridine Synthesis PDF Author: Xiao-Feng Wu
Publisher: Elsevier
ISBN: 0128093684
Category : Science
Languages : en
Pages : 91

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Book Description
Transition Metal-Catalyzed Pyridine Synthesis provides an overview of pyridines, describing properties of these heterocycle compounds and describing traditional synthetic procedures for them. The book then explores catalyzed procedures for pyridine synthesis in greater detail and depth than is currently available in published Review articles. The short series Transition Metal-Catalyzed Heterocycles Synthesis, authored by Xiao-Feng Wu, summarizes recent achievements on heterocycles synthesis with transition metal as the catalysts, with each volume dedicated to one heterocycle compound. - Brief, focused review of this active research area, Pyridine synthesis via transition metal catalysis - Useful coverage of Pyridine properties and both intermolecular and intramolecular cyclization - Volume Two in Elsevier's short work series, "Transition Metal-Catalyzed Heterocycles Synthesis"

Pyridine and Its Derivatives, Volume 14, Part 1

Pyridine and Its Derivatives, Volume 14, Part 1 PDF Author: Erwin Klingsberg
Publisher: John Wiley & Sons
ISBN: 0470188146
Category : Science
Languages : en
Pages : 626

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Book Description
The Chemistry of Heterocyclic Compounds, since its inception, has been recognized as a cornerstone of heterocyclic chemistry. Each volume attempts to discuss all aspects – properties, synthesis, reactions, physiological and industrial significance – of a specific ring system. To keep the series up-to-date, supplementary volumes covering the recent literature on each individual ring system have been published. Many ring systems (such as pyridines and oxazoles) are treated in distinct books, each consisting of separate volumes or parts dealing with different individual topics. With all authors are recognized authorities, the Chemistry of Heterocyclic Chemistry is considered worldwide as the indispensable resource for organic, bioorganic, and medicinal chemists.

Pyridines: From Lab to Production

Pyridines: From Lab to Production PDF Author: Eric F.V. Scriven
Publisher: Academic Press
ISBN: 0123852366
Category : Science
Languages : en
Pages : 583

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Book Description
Pyridines: From Lab to Production provides a synthetic armory of tools to aid the practicing chemist by reviewing the most reliable historical methods alongside new methods/ Written by scientists who have actually used these in synthesis. By emphasizing tricks and tips to optimize reactions for the best yields and purity, which are often missing from the primary literature, this book provides another dimension for the synthetic chemist. A combined academic and industrial approach evaluates the best methods for different scales of reaction and discusses practical tips (e.g. when to stop a reaction early to maximize purity or when to re-use side products). Chapters also assess whether to make or source starting materials, how to connect them and what are the best synthetic routes. The book is designed to be a stand-alone reference, but also provides cross references to leading reviews and the Comprehensive Heterocyclic Chemistry reference works for those who want to learn more. - Reviews tried and tested practical methods to help the reader select the best method for their research - Includes tips, tricks and hints to enable the reader to get the best yield or cleanest product out of their reaction for synthesising or transforming a pyridine derivative - Written by both academic researchers and industry leaders this provides a unique view of how to get the most out of a reaction no matter what scale you are running this on