Download or read book Palladium catalyzed Carbonylation of Unsaturated Carbon carbon Bonds written by Ji Yang and published by . This book was released on 2020 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis is mainly concerned with the carbonylative functionalization of unsaturated organic substrates in the presence of homogeneous catalysts. More specifically, oxidative carbonylation of alkynes, alkoxycarbonylation of 1,3-dienes and platinum-catalyzed alkoxycarbonylation of olefins are presented. The resulting esters, maleimides and adipic acid diesters constitute important intermediates for both organic synthesis and chemical industry. Regarding methodology developments, firstly a catalytic oxidative carbonylation reaction with air as a green oxidant was developed.eng

Download or read book Palladium Catalyzed Oxidation of Hydrocarbons written by P. Henry and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 449 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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!.

Download or read book Synthesis and Palladium catalyzed Carbonylation of Substituted Vinyl Triflates written by Adam Gerherd). Meyer and published by . This book was released on 1995 with total page 360 pages. Available in PDF, EPUB and Kindle. Book excerpt: Studies the synthesis of substituted hydraxy and amino vinyl triflates and their applicability to undergo an intramolecular palladium-catalyzed carbonylation reaction. Optically active monocyclic and bicyclic [alpha], [beta]-unsaturated [ga-lactones and the monoterpene(+) mintlactone were synthesized.

Download or read book Palladium Catalyzed Carbon carbon Bond Formation at Carbon hydrogen Bonds written by Louis-Charles Campeau and published by . This book was released on 2008 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: The biaryl core has been identified by medicinal chemists as a privileged structure in pharmaceutical compounds as it is found in 4.3% of all drugs. For over a century, synthetic chemists have sought new methods for their preparation. Breakthroughs in synthetic catalytic methodology over the past thirty years gave rise to now routine reactions such as the Suzuki and Stille couplings. Unfortunately, the need for pre-activation of both coupling partners makes for wasteful installation and subsequent removal of activating agents. Direct arylation reactions are attractive alternatives to traditional cross-coupling methods, as one of the pre-activated partners is replaced with a simple arene. The organometallic coupling partner is typically replaced as it is the most difficult to prepare. Although the advantages of this approach have made it a popular research topic for more than twenty-five years, no general catalysts exist for this transformation, and in a lot of cases reactivity remains a challenge. This thesis will outline our work in this area of research. First, our efforts toward the development of a general catalyst for the intramolecular direct arylation of aryl halides with simple arenes will be presented. These studies led to the development of three new catalysts for this transformation, affording a process general for aryl chlorides, bromides and iodides. Additionally, mechanistic studies performed on this system have brought to the forefront the concerted metallation-deprotonation mechanistic model for direct arylation. Ultimately, these studies led to the first non-directed intermolecular direct arylation of a simple arene. In a second section, efforts toward the inclusion of pi-deficient heteocycles as a substrate class in direct arylation will be outlined. These studies led to the development of a novel cross-coupling reaction of azine N-oxides with aryl halides. Greater mechanistic understanding, made possible through the use of computational tools, was crucial in extending this methodology to azole N-oxides. Finally, the development of novel direct functionalization reactions with picoline derivatives is described. These substrates are among the first to be suitable for catalyst controlled site-selective functionalization of a sp2 or sp3 C-H bond.

Download or read book Handbook of Organopalladium Chemistry for Organic Synthesis written by Ei-ichi Negishi and published by John Wiley & Sons. This book was released on 2003-11-24 with total page 1657 pages. Available in PDF, EPUB and Kindle. Book excerpt: Organized to provide maximum utility to the bench synthetic chemist. The editor is well-known for his work in exploring, developing, and applying organopalladium chemistry. Contributors include over 24 world authorities in the field.

Download or read book Advances in Palladium catalyzed Carbon carbon Bond Formation Via Functionaliszaton of Carbon hydrogen Bonds written by Olivier René and published by . This book was released on 2010 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Catalytic Carbonylation Reactions written by Matthias Beller and published by Springer Science & Business Media. This book was released on 2006-09-14 with total page 289 pages. Available in PDF, EPUB and Kindle. Book excerpt: Carbonylation reactions are of major importance in both organic and industrial chemistry. Due to the availability, price and reactivity pattern, carbon monoxide is becoming a more and more important building block for fine and bulk chemicals. The major reaction types of carbon monoxide are comprehensively discussed by leading experts from academia and industry. The authors highlight important carbonylation reactions such as hydroformylation, alkoxy-carbonylations, co/olefin-copolymerization, Pauson-Khand reactions and others. They illustrate applications in organic synthesis and give industrial examples. This volume is designed to provide graduate students and researchers with essential information on the use of carbon monoxide in organic synthesis. Therefore, the reader will get a balanced view of this developing and complex subject.

Download or read book The Chemical Transformations of C1 Compounds written by Xiao-Feng Wu and published by John Wiley & Sons. This book was released on 2022-01-14 with total page 1780 pages. Available in PDF, EPUB and Kindle. Book excerpt: The Chemical Transformations of C1 Compounds A comprehensive exploration of one-carbon molecule transformations The chemistry of one-carbon molecules has recently gained significant prominence as the world transitions away from a petroleum-based economy to a more sustainable one. In The Chemical Transformations of C1 Compounds, an accomplished team of chemists delivers an in-depth overview of recent developments in the field of single-carbon chemistry. The three-volume book covers all major C1 sources, including carbon monoxide, carbon dioxide, methane, methanol, formic acid, formaldehyde, carbenes, C1 halides, and organometallics. The editors have included resources discussing the main reactions and transformations into feedstock chemicals of each of the major C1 compounds reviewed in dedicated chapters. Readers will discover cutting-edge material on organic transformations with MeNO2, DMF, DCM, methyl organometallic reagents, CCl4, CHCl3, and CHBr3, as well as recent achievements in cyanation reactions via cross-coupling. The book also offers: Thorough introductions to chemical transformations of CH4, methods of CH4 activation, chemical transformations of CH3OH and synthesis alkenes from CH3OH Comprehensive explorations of the carbonylation of MeOH, CH2O in organic synthesis, organic transformations of HCO2H, and hydrogen generation from HCO2H Practical discussions of the carbonylation of unsaturated bonds with heterogeneous and homogeneous catalysts, as well as the carbonylation of C(sp2)-X bonds and C(sp3)-X bonds In-depth examinations of carbonylative C-H bond activation and radical carbonylation Perfect for organic and catalytic chemists, The Chemical Transformations of C1 Compounds is also an ideal resource for industrial chemists, chemical engineers, and practitioners at energy supply companies.

Download or read book Development of New Classes of Palladium and Nickel Catalyzed Carbonylation Reactions written by Jevgenijs Tjutrins and published by . This book was released on 2017 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: "This thesis describes the development of new palladium and nickel catalyzed carbonylation reactions to efficiently and rapidly generate products with minimal waste. These reactions can be carried out using commercially and/or readily available starting materials, including imines, acid chlorides, aryl iodides, alkynes, alkenes and carbon monoxide. In chapter 2, we describe a palladium catalyzed carbonylative synthesis of polysubstituted imidazoles. This transformation involves a tandem catalytic process, where a single palladium catalyst mediates both the carbonylation of aryl halides to form acid chlorides, as well as cyclocarbonylation of a-chloroamides, to generate 1,3-dipoles. Finally, a regioselective 1,3-dipolar cycloaddition with electron poor imines furnishes tetra-substituted imidazoles. Overall this provides a route to prepare imidazoles from five readily available building blocks: two electronically distinct imines, aryl halides and two molecules of CO. In chapter 3, we describe a nickel catalyzed approach to synthesize of isoindolinones via the carbonylation of aryl iodides in the presence of imines. In this, the nickel catalyzed in situ generation of acid chlorides via aryl halide carbonylation allows the formation of a chloroamides, which in turn undergo an intramolecular cyclization to form isoindolinones. This reaction offers an efficient alternative to traditional syntheses of isoindolinones, which often require the initial assembly of the appropriate aryl-tethered precursors for cyclization. In chapter 4, we describe the development of a palladium catalyzed, electrophilic approach to the carbonylative C-H bond functionalization of a range of heterocycles. Mechanistic studies show that the Pd/PtBu3 catalyst can mediate the in situ formation of highly electrophilic aroyl iodide intermediates, which react with heterocycles forming aryl-(hetero)aryl ketones. This provides a general methodology to construct ketones from aryl iodides and electron rich heterocycles without the need to prefunctionalize the heterocycle, install directing groups, or exploit high energy starting materials (e.g. acid chlorides). Chapter 5 describes mechanistic studies on the palladium catalyzed multicomponent synthesis of 1,3-oxazolium-5-olates (Münchnones). Previous work in our laboratory has shown that Münchnones can be generated via the palladium catalyzed multicomponent coupling of acid chlorides, imines and CO. In order to better understand this reaction, we synthesized and characterized key reactive intermediates, studied stoichiometric model reactions, and performed kinetic studies on catalytic reaction. These allowed the elucidation of the role of the catalyst structure, rate determining steps, as well as the importance of off cycle steps in this transformation. In chapter 6, we show how the mechanistic insights laid out in the previous chapter can be applied to create a highly active catalytic system for synthesis of 1,3-oxazolium-5-olates. By employing a sterically encumbered pyrrole-based phosphine ligand, which can be more easily displaced by carbon monoxide for carbonylation, we have created a catalyst that is more than ten times more active that previous systems for this reaction. When coupled with alkyne cycloaddition, this offers a broadly generalizable route to form polysubstituted pyrroles from simple imines, acid chlorides and alkynes. This approach has been applied to the multicomponent synthesis of Atorvastatin (i.e., Lipitor). " --

Download or read book Chelation assisted Palladium catalyzed Activation of C H Bonds written by Ramesh Giri and published by . This book was released on 2009 with total page 1280 pages. Available in PDF, EPUB and Kindle. Book excerpt: Carbon-hydrogen (C-H) bonds are ubiquitous in organic molecules. Utilization of such abundant chemical moieties as functional group equivalents could shorten route to synthetic targets and provide chemists with new disconnections in retrosynthesis. As such regio- and stereoselective functionalization of unactivated C-H bonds has remained one of the major challenges in organic chemistry. The majority of the transition metals have been rigorously examined for their efficacy in transforming unactivated C-H bonds (pKa >35) into useful functional groups or into C-C bonds. Among those metals, palladium is particularly effective in activating both aromatic (sp2) and aliphatic (sp3) C-H bonds. This thesis explores the reactivity of palladium catalysts in both of these areas. The research herein was conducted using directing groups for C-H cleavage with special focus on utilizing simple functionality such as carboxylic acids. Chapter one details different types of directing groups and their utility in a variety of reactions. Chapters two and three contain details of research on C-heteroatom (C-I and C-O) and C-C bond formation, respectively, with palladium acetate as a catalyst. The iodination and acetoxylation reactions proceed under mild conditions and moderate to excellent levels of diastereoselectivity (up to 99.9%) have been observed with both sp2 and sp3 C-H bonds using oxazoline as the directing group. Mechanistic investigations have been carried out in order to understand the high level of stereoselection and, in this process, a number of palladacycle intermediates have been characterized by X-ray crystallography which led us to assign the absolute stereochemistry of C-H activation. Moreover, the iodination protocol could also be extended to prepare diiodides as intermediates for cyclopropanation which provides a new disconnection approach to construct cyclopropanes. Chapter two discusses C-C bond formation via cross-coupling reactions with organoboron reagents and carbon monoxide using the carboxylic acids as the directing group. Detailed mechanistic investigation along with characterization of intermediate palladacycle formed from sodium toluate have revealed an unprecendented directing ability of carboxylate groups in which the carbonyl oxygen, rather than the O-anion, directs palladium for C-H cleavage.

Download or read book Strategies for Palladium Catalyzed Non directed and Directed C bond H Bond Functionalization written by Anant R. Kapdi and published by Elsevier. This book was released on 2017-05-23 with total page 502 pages. Available in PDF, EPUB and Kindle. Book excerpt: Strategies for Palladium-Catalyzed Non-directed and Directed C-H Bond Functionalization portrays the complete scope of these two aspects of C-H bond functionalization in a single volume for the first time. Featured topics include the influence of palladacyclic systems in C-H bond functionalization (need for newer catalytic systems for better efficiency), mechanistic aspect of the functionalization strategies leading to better systems, and applications of these methodologies to natural product synthesis and material synthesis. Addresses the involvement of catalytic systems (palladacycles) for better functionalization of (hetero)arenes to emphasize the need for developing better, more selective systems Covers the use of powerful mechanistic tools for understanding and assisting the development of better functionalization strategies Discusses the finer aspects of C-H bond functionalization, such as control of regioselectivity with or without directing groups Includes a chapter detailing the synthesis of naturally occurring molecules or functional molecules via both pathways for assessing the applicability of the functionalization strategies

Download or read book Catalytic Reactions written by Peter Maitlis and published by Elsevier. This book was released on 2012-12-02 with total page 233 pages. Available in PDF, EPUB and Kindle. Book excerpt: The Organic Chemistry of Palladium, Volume I1: Catalytic Reactions deals with organic transformations resulting from palladium complexes either stoichiometrically or catalytically. One feature of a reaction catalyzed by transition metals is the absence of evidence for the typical reactive intermediates of organic chemistry, carbanions, and carbonium ions. This lack of evidence is due to the metal acting both as a source and a sink of electrons that result in energetically unfavorable ionic intermediaries. The book explains that palladium (II) can induce C-O bond formation. These reactions involve oxidation of the organic substrate and reduces the Pd(II) to metal, and are not catalytic. Industrial applications can re-oxidize the palladium metal back to Pd(II) in situ, making the reactions catalytic. The text also discusses certain reactions that can form C-O bonds as part of an oxidative process. The book also describes significant reactions that can be catalyzed by palladium metal, such as in the hydrogenation of multiple bonds, in the carbonylation of certain olefins and acetylenes, and in the catalytic cracking of high molecular weight hydrocarbons. Organic chemists, analytical chemists, investigators, and scientists whose works involve physical or inorganic chemistry will find the book truly useful.

Download or read book Advances in Palladium catalyzed Carbon carbon Bond Formation Via Functionaliszaton of Carbon hydrogen Bonds written by Olivier René and published by . This book was released on 2010 with total page 212 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Modern Carbonylation Methods written by László Kollár and published by John Wiley & Sons. This book was released on 2008-06-25 with total page 383 pages. Available in PDF, EPUB and Kindle. Book excerpt: Comprehensively covering modern carbonylation chemistry, this book is an indispensable companion for all synthetic chemists working in industry and academia. This monograph contains everything there is to know from recent advances in the investigation of carbonylation catalysts, via coordination chemistry to the synthetic application of transition metal catalyzed carbonylations.

Download or read book Comprehensive Inorganic Chemistry II written by and published by Newnes. This book was released on 2013-07-23 with total page 7694 pages. Available in PDF, EPUB and Kindle. Book excerpt: Comprehensive Inorganic Chemistry II, Nine Volume Set reviews and examines topics of relevance to today’s inorganic chemists. Covering more interdisciplinary and high impact areas, Comprehensive Inorganic Chemistry II includes biological inorganic chemistry, solid state chemistry, materials chemistry, and nanoscience. The work is designed to follow on, with a different viewpoint and format, from our 1973 work, Comprehensive Inorganic Chemistry, edited by Bailar, Emeléus, Nyholm, and Trotman-Dickenson, which has received over 2,000 citations. The new work will also complement other recent Elsevier works in this area, Comprehensive Coordination Chemistry and Comprehensive Organometallic Chemistry, to form a trio of works covering the whole of modern inorganic chemistry. Chapters are designed to provide a valuable, long-standing scientific resource for both advanced students new to an area and researchers who need further background or answers to a particular problem on the elements, their compounds, or applications. Chapters are written by teams of leading experts, under the guidance of the Volume Editors and the Editors-in-Chief. The articles are written at a level that allows undergraduate students to understand the material, while providing active researchers with a ready reference resource for information in the field. The chapters will not provide basic data on the elements, which is available from many sources (and the original work), but instead concentrate on applications of the elements and their compounds. Provides a comprehensive review which serves to put many advances in perspective and allows the reader to make connections to related fields, such as: biological inorganic chemistry, materials chemistry, solid state chemistry and nanoscience Inorganic chemistry is rapidly developing, which brings about the need for a reference resource such as this that summarise recent developments and simultaneously provide background information Forms the new definitive source for researchers interested in elements and their applications; completely replacing the highly cited first edition, which published in 1973

Download or read book Palladium Catacyzed Carbonylative Approaches to Acyl Electrophiles Using Ligand Effects Or Visible Light written by Yi Liu and published by . This book was released on 2021 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: "Transition metal catalyzed carbonylation reactions have been broadly exploited for the synthesis of carbonyl-containing products. A versatile version of these are palladium-catalyzed carbonylative coupling reactions of organic halides and nucleophiles. However, one drawback to this chemistry is the low electrophilic reactivity of the palladium-acyl intermediates in reaction, which severely limits the scope of nucleophiles that can be employed in carbonylations. This thesis describes studies to address this challenge by the formation of potent acyl electrophiles via metal-catalyzed carbonylations, and their use with non-classical carbonylation nucleophiles. In chapter 2, we demonstrate how the correctly ligated palladium catalyst can be used to create potent acyl-pyridinium electrophiles via the carbonylation of aryl or vinyl triflates, and use these for in situ (hetero)arene C-H bond functionalization. The reaction was catalyzed by a Xantphos-coordinated palladium catalyst, and the bidentate and large-bite-angle ligand is believed to balance the activation of the strong C(sp2)-OTf bonds with the reductive elimination of reactive N-acyl-pyridinium electrophiles. The pyridine employed not only leads to the formation of the acyl-pyridinium salt electrophile, but its structure can be used to modulate selectivity in arene C-H functionalization. Overall, this offers a carbonylative method to form diaryl ketones, [alpha],[beta]-unsaturated ketones, and polycyclic ketones using a broad range of aryl- or vinyl- triflates and (hetero)arenes. Chapter 3 describes an extension of the work in chapter 2, where simple lithium chloride rather than the specialized trifluoromethyl- or methoxy-substituted pyridine can be used as the additive for the palladium catalyzed carbonylative coupling of aryl or vinyl triflates and heteroarenes to form ketones. Mechanistic studies suggest the reaction proceeds by the catalytic generation of acid chloride electrophiles for functionalization of electron-rich heterocycles.A limitation to the carbonylative generation of acyl electrophiles noted above is the need to use aryl- or vinyl-(pseudo)halides as reagents. The association of carbon monoxide to the catalyst severely inhibits oxidative addition reactions, and blocks the use of less reactive substrates such as alkyl halides. In chapter 4, we design a strategy to address these challenges using visible light excitation of palladium. This has opened an approach to perform the carbonylation of diverse array of aryl- and even alkyl-halides and from these build-up acid chlorides with the ability to reaction with various nucleophiles. Mechanistic studies suggest the reaction proceeds via a unique combination of photoevents, where the photoexcitation of Pd(0) induces electron transfer with the organic halide to favor oxidative addition, while the photoexcitation of the Pd(II) intermediate leads to Pd-acyl bond scission and the ultimate reductive elimination of acid chloride electrophiles. While the results in chapter 4 expand the variety of products available from carbonylation, the formation of acid chlorides as reaction products (rather than intermediates) is usually not possible. The latter can be attributed to the high reactivity of acid chlorides, which can lead to their rapid re-addition to the palladium catalyst and either inhibit the reaction or lead to their slow decomposition. In chapter 5, we developed a method to address these limits via the synthesis of less easily reduced acyl fluorides. In this case, mechanistic studies suggest visible light favored oxidative addition to Pd(0) is coupled with rapid ligand driven reductive elimination of the acyl fluoride product, which does not re-add to the Pd(0) once formed. By driving these two reverse steps with different inputs, this has offered a general platform to access acyl fluoride electrophiles, and from these synthesize complex, highly functionalized carbonyl-containing products"--

Download or read book Palladium Catalyzed Alternating Cooligomerization of Ethylene and Carbon Monoxide to Unsaturated Ketones written by Wilhelm Keim and published by . This book was released on 2012 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: