Author: Edwin G. Avila (Graduate student)
Publisher:
ISBN:
Category : Alkenes
Languages : en
Pages : 52
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Book Description
Conventionally, the Tsuji-Wacker oxidation has been used to promote the Markovnikov oxidation of terminal alkenes to their respective ketones in the presence of dioxygen. Recently, the regioselective formation of the aldehyde via an anti-Markovnikov addition, which is of substantial importance to the chemistry community, has been demonstrated using a palladium/nitrite catalyst. Herein, we demonstrate the potential for the regioselective transformation of allylbenzene derivatives to their respective aldehydes under green catalytic conditions via the use of palladium nanoparticles in water. The same Pd nanoparticle catalysts were also investigated for the homocoupling of phenyl boronic acids under aerobic conditions. Catalysis results were examined using 1H NMR and/or GC-MS analyses.
Author: Christos Nixarlidis
Publisher:
ISBN:
Category : Catalysis
Languages : en
Pages : 55
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Book Description
Abstract: The field of nanomaterials has been getting more attention the last few decades because of their unique optical, electrical and physical properties compared to those of bulk materials of the same type. One of the most studied nanomaterials is colloidal metal nanoparticles (NP) because of the tunability to control their structural parameters such as core size, shape, and chemical functionality using organic capping ligands. The head group of these ligands interacts with the surface of the metal nanoparticle whereas the organic chain of the ligand prevents aggregation and the terminal group controls the chemical properties such as solubility and chemical interactions. The synthesis of water-soluble alkanethiolate-capped palladium nanoparticle (PdNP) was achieved using the thiosulfate protocol developed by our group. The produced PdNP is characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), 1H NMR and UV-Vis Spectroscopy.
Author: Ning Jiao
Publisher: John Wiley & Sons
ISBN: 1119304040
Category : Science
Languages : en
Pages : 701
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Book Description
A valuable introduction to green oxidation for organic chemists interested in discovering new strategies and new reactions for oxidative synthesis Green Oxidation in Organic Synthesis provides a comprehensive introduction and overview of chemical preparation by green oxidative processes, an entry point to the growing journal literature on green oxidation in organic synthesis. It discusses both experimental and theoretical approaches for the study of new catalysts and methods for catalytic oxidation and selective oxidation. The book highlights the discovery of new reactions and catalysts in recent years, discussing mechanistic insights into the green oxidative processes, as well as applications in organic synthesis with significant potential to have a major impact in academia and industry. Chapters are organized according to the functional groups generated in the reactions, presenting interesting achievements for functional group formation by green oxidative processes with O2, H2O2, photocatalytic oxidation, electrochemical oxidation, and enzymatic oxidation. The mechanisms of these novel transformations clearly illustrated. Green Oxidation in Organic Synthesis will serve as an excellent reference for organic chemists interested in discovering new strategies for oxidative synthesis which address the priorities of green and sustainable chemistry.
Author: Vivek Polshettiwar
Publisher: John Wiley & Sons
ISBN: 1118609808
Category : Technology & Engineering
Languages : en
Pages : 670
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Book Description
Exhibiting both homogeneous and heterogeneous catalytic properties, nanocatalysts allow for rapid and selective chemical transformations, with the benefits of excellent product yield and ease of catalyst separation and recovery. This book reviews the catalytic performance and the synthesis and characterization of nanocatalysts, examining the current state of the art and pointing the way towards new avenues of research. Moreover, the authors discuss new and emerging applications of nanocatalysts and nanocatalysis, from pharmaceuticals to fine chemicals to renewable energy to biotransformations. Nanocatalysis features contributions from leading research groups around the world. These contributions reflect a thorough review of the current literature as well as the authors’ first-hand experience designing and synthesizing nanocatalysts and developing new applications for them. The book’s nineteen chapters offer a broad perspective, covering: Nanocatalysis for carbon-carbon and carbon-heteroatom coupling reactions Nanocatalysis for various organic transformations in fine chemical synthesis Nanocatalysis for oxidation, hydrogenation, and other related reactions Nanomaterial-based photocatalysis and biocatalysis Nanocatalysts to produce non-conventional energy such as hydrogen and biofuels Nanocatalysts and nano-biocatalysts in the chemical industry Readers will also learn about the latest spectroscopic and microscopy tools used in advanced characterization methods that shed new light on nanocatalysts and nanocatalysis. Moreover, the authors offer expert advice to help readers develop strategies to improve catalytic performance. Summarizing and reviewing all the most important advances in nanocatalysis over the last two decades, this book explains the many advantages of nanocatalysts over conventional homogeneous and heterogeneous catalysts, providing the information and guidance needed for designing green, sustainable catalytic processes.
Author: David S. Phaho
Publisher:
ISBN:
Category : Transition metals
Languages : en
Pages : 494
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Book Description
Author: P. Henry
Publisher: Springer Science & Business Media
ISBN: 940099446X
Category : Science
Languages : en
Pages : 449
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Book Description
The field of organometallic chemistry has emerged over the last twenty-five years or so to become one of the most important areas of chemistry, and there are no signs of abatement in the intense current interest in the subject, particularly in terms of its proven and potential application in catalytic reactions involving hydrocarbons. The development of the organometallic/ catalysis area has resulted in no small way from many contributions from researchers investigating palladium systems. Even to the well-initiated, there seems a bewildering and diverse variety of organic reactions that are promoted by palladium(II) salts and complexes. Such homogeneous reactions include oxidative and nonoxidative coupling of substrates such as olefins, dienes, acetylenes, and aromatics; and various isomerization, disproportionation, hydrogenation, dehydrogenation, car bonylation and decarbonylation reactions, as well as reactions involving formation of bonds between carbon and halogen, nitrogen, sulfur, and silicon. The books by Peter M. Maitlis - The Organic Chemistry of Palladium, Volumes I, II, Academic Press, 1971 - serve to classify and identify the wide variety of reactions, and access to the vast literature is available through these volumes and more recent reviews, including those of J. Tsuji [Accounts Chem. Res. , 6, 8 (1973); Adv. in Organometal. , 17, 141 (1979)], R. F. Heck [Adv. in Catat. , 26, 323 (1977)], and ones by Henry [Accounts Chem. Res. , 6, 16 (1973); Adv. in Organometal. , 13, 363 (1975)]. F. R. Hartley's book - The Chemistry of Platinum and Palladium, App!. Sci. Pub!.
Author: Caitlin Kozack
Publisher:
ISBN:
Category :
Languages : en
Pages : 221
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Book Description
Palladium-catalyzed allylic C-H acetoxylation has been the subject of significant study in its 60-year history, however several limitations still exist. There are no methods for the allylic acetoxylation of terminal alkenes that exhibit high catalytic turnover. This is of considerable interest in order to establish large scale reactions. Reactions with a broad scope in substrate and coupling partner are also relatively sparse. In order for the field to continue to move forward, it is critical to understand the mechanistic systems so the insights can be applied to develop new methods that are broad in scope and robust in catalytic activity. This thesis will focus on mechanistic investigations to understand the mechanism of 4,5-diazafluoren-one (DAF)/Pd(OAc)[2]-catalyzed aerobic allylic C-H acetoxylation reactions, as well as develop methods that will expand the scope and increase the catalytic activity of allylic acetoxylation.Chapter 1 analyzes high turnover methods for Pd-catalyzed allylic acetoxylation with a focus on the factors that contribute to the success of existing catalytically robust methods, as well as the challenges with developing high turnover methods for terminal akenes and how recent advances with this substrate class may provide insights into unlocking reactivity. Chapter 2 presents the development of a method for Pd-catalyzed aerobic allylic acyloxylation with a low stoichiometry of carboxylic acid coupling partners. Chapter 3 provides an in-depth mechanistic investigation into 4,5-diazafluoren-9-one (DAF)/Pd(OAc)[2]-catalyzed aerobic allylic C-H acetoxylation by using operands spectroscopy to elucidate the two distinct rate regimes. Chapter 4 probes the role of benzoquinone additives in DAF/Pd(OAc)[2]-catalyzed aerobic allylic acetoxylation in the presence and absence of Co(salophen), a transition metal cocatalyst. Chapter 5 presents the development of a method for high turnover DAF/Pd(OAc)[2]-catalyzed allylic C-H acetoxylation of a terminal alkene as well as preliminary kinetics to probe the mechanism.
Author: Ashok Kumar
Publisher:
ISBN:
Category : Electrochemistry
Languages : en
Pages : 115
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Book Description
Palladium metal in its various forms has been heavily studied for many catalytic, hydrogen storage and sensing applications and as an electrocatalyst in fuel cells. A short review on various applications of palladium and the mechanism of Pd nanoparticles synthesis will be discussed in chapter 1. Size dependent properties of various metal nanoparticles and a thermodynamic theory proposed by Plieth to predict size dependent redox properties of metal nanoparticles will also be discussed in chapter 1. To evaluate size dependent stability of metal nanoparticles using electrochemical techniques in aqueous media, a synthetic route was designed to produce water soluble Pd nanoparticles. Also, a purification technique was developed to obtain monodisperse metal nanoparticles to study size dependent stability using electrochemical methods. Chapter 2 will describe in detail the synthesis, characterization and size dependent anodic dissolution studies of water soluble palladium nanoparticles.The cost associated with using expensive metal catalysts can further decreased by using the underpotential deposition (UPD) technique, in which one metal is electrodeposited in monolayer or submonolayer form on a different metal substrate. Electrochemically, this process can be detected by the presence of a deposition peak positive to the bulk deposition potential in a cyclic voltammetry (CV) experiment. The difference between the bulk deposition potential and underpotential deposition peak (i.e. the UPD shift), which is a measure of the energetics of the monolayer deposition step, depends on the work function difference between the metal pairs. Chapter 3 will explore how metal nanoparticles of different sizes will change the energetics of the UPD phenomenon, using the UPD of Cu on palladium nanoparticles as an example. It will be shown that the UPD shift depends on the size of the nanoparticle substrate in a way that is understandable based on the Plieth model.High electrocatalytic activity of palladium towards ethanol oxidation in an alkaline medium makes it an ideal candidate for the anode electrocatalyst in direct ethanol based fuel cells (DEFCs). Chapter 4 will explore the poisoning of the catalytic activity of palladium in the presence of halide impurities, often used in synthesis of palladium nanoparticles as precursors or shape directing agents.
Author: Lukas J. Gooßen
Publisher: Springer
ISBN: 3642342868
Category : Science
Languages : en
Pages : 345
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Book Description
Barry Trost: Transition metal catalyzed allylic alkylation.- Jeffrey W. Bode: Reinventing Amide Bond Formation.- Naoto Chatani and Mamoru Tobisu: Catalytic Transformations Involving the Cleavage of C-OMe Bonds.- Gregory L. Beutner and Scott E. Denmark: The Interplay of Invention, Observation and Discovery in the Development of Lewis Base Activation of Lewis Acids for Catalytic Enantioselective Synthesis.- David R. Stuart and Keith Fagnou: The Discovery and Development of a Palladium(II)-Catalyzed Oxidative Cross-Coupling of Two Unactivated Arenes.- Lukas Gooßen and Käthe Gooßen: Decarboxylative Cross-Coupling Reactions.- A. Stephen K. Hashmi: Gold-Catalyzed Organic Reactions.- Ben List: Developing Catalytic Asymmetric Acetalizations.- Steven M. Bischof, Brian G. Hashiguchi, Michael M. Konnick, and Roy A. Periana: The De NovoDesign of CH Bond Hydroxylation Catalysts.- Benoit Cardinal-David, Karl A. Scheidt: Carbene Catalysis: Beyond the Benzoin and Stetter Reactions.- Kenso Soai and Tsuneomi Kawasaki: Asymmetric autocatalysis of pyrimidyl alkanol.- Douglas C. Behenna and Brian M. Stoltz: Natural Products as Inspiration for Reaction Development: Catalytic Enantioselective Decarboxylative Reactions of Prochiral Enolate Equivalents. Hisashi Yamamoto: Acid Catalysis in Organic Synthesis.
Author: Matthew Scott McCammant
Publisher:
ISBN:
Category : Alkenes
Languages : en
Pages : 180
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Book Description
