Download or read book Computational Investigations of Pd Catalyzed C H Functionalization Reactions written by Katherine Lynn Bay and published by . This book was released on 2020 with total page 138 pages. Available in PDF, EPUB and Kindle. Book excerpt: The use of an inert C-H bond towards the generation of a functional group is advantageous, as these bonds are the most abundant chemical moieties in organic molecules. A one-step conversion of a C-H bond to the desired functionality reduces the number of synthetic steps, which in turn minimizes the use of costly reagents, solvent, and time. Selective activation of a particular C-H bond in an organic molecule where C-H bonds are ubiquitous, however, is a challenging task. Among the most challenging aspects of developing robust C-H functionalization methodologies is identifying catalyst and reagent combinations capable of site-selective as well as stereoselective reactions. Therefore, directed C-H bond functionalization using a directing group and a suitable transition metal is of current interest. Palladium complexes are highly selective and have shown efficiency in various areas of organic synthesis, which make palladium catalysts particularly useful in the field of C-H functionalization. Palladium is incredibly powerful for the construction of carbon-carbon and carbon-heteroatom bonds by C-H activation of aryl and alkyl groups. Palladium-catalyzed ligand-directed C-H functionalization is a key goal towards the synthesis of complex multifunctional substrates. Understanding the mechanism and origins of stereoselectivity of palladium-catalyzed C-H functionalization reactions is essential to progress this field. The collaboration between experiment and computations has provided a deeper mechanistic understanding and insight than any of the isolated techniques can provide. Kinetics and isolation of intermediates provide information on mechanistic pathways, while computations can provide details of both structures and energetics in specific steps in the whole catalytic cycle. Computations have become vital to elucidate structures of molecules, mechanisms, and selectivities of reactions. Due to the rapid development of hardware, software, and theoretical methods, computational chemistry has evolved into a very powerful and routine tool to study complex mechanisms. The work in this thesis has stemmed from several collaborations through the NSF Center for Selective C-H Functionalization (CCHF), which is comprised of synthetic methodologists, physical organic chemists, catalyst developers, enzymologists, computational chemists, and several partners in the pharmaceutical industry. Motivated by the potential of understanding C-H functionalization transformations in order to promote the development of new reactions, this thesis focuses on using computational methods to understand systems of relevance to C-H activation using palladium as a catalyst. Early projects aim to use computations to make proposed models for nonlinear effects to serve as a meaningful mechanistic probe for predicting reaction kinetics (Chapters 1-2). The second section delves into elucidating the mechanisms as well as the role of various substrates, ligands, and oxidants, particularly silver (I) acetate, on how each particular reaction is performed (Chapters 3-6). Later in this thesis, the focus diverges to highlight the elucidation of an enantioselective -C-H functionalization where stereoselectivity arises from attractive aryl-aryl interactions (Chapter 7).
Download or read book Mechanistic Studies on Transition Metal Catalyzed C H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods written by Gui-Juan Cheng and published by Springer. This book was released on 2017-06-07 with total page 140 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis presents detailed mechanistic studies on a series of important C-H activation reactions using combined computational methods and mass spectrometry experiments. It also provides guidance on the design and improvement of catalysts and ligands. The reactions investigated include: (i) a nitrile-containing template-assisted meta-selective C-H activation, (ii) Pd/mono-N-protected amino acid (MPAA) catalyzed meta-selective C-H activation, (iii) Pd/MPAA catalyzed asymmetric C-H activation reactions, and (iv) Cu-catalyzed sp3 C-H cross-dehydrogenative-coupling reaction. The book reports on a novel dimeric Pd-M (M = Pd or Ag) model for reaction (i), which successfully explains the meta-selectivity observed experimentally. For reaction (ii), with a combined DFT/MS method, the author successfully reveals the roles of MPAA ligands and a new C-H activation mechanism, which accounts for the improved reactivity and high meta-selectivity and opens new avenues for ligand design. She subsequently applies ion-mobility mass spectrometry to capture and separate the [Pd(MPAA)(substrate)] complex at different stages for the first time, providing support for the internal-base model for reaction (iii). Employing DFT studies, she then establishes a chirality relay model that can be widely applied to MPAA-assisted asymmetric C-H activation reactions. Lastly, for reaction (iv) the author conducts detailed computational studies on several plausible pathways for Cu/O2 and Cu/TBHP systems and finds a reliable method for calculating the single electron transfer (SET) process on the basis of benchmark studies.
Download or read book Metal catalyzed Cross coupling Reactions written by François Diederich and published by John Wiley & Sons. This book was released on 2008-07-11 with total page 540 pages. Available in PDF, EPUB and Kindle. Book excerpt: Carbon-carbon bond forming reactions are arguably the most important processes in chemistry, as they represent key steps in the building of complex molecules from simple precursors. Among these reactions, metal-catalyzed cross-coupling reactions are extensively employed in a wide range of areas of preparative organic chemistry, ranging from the synthesis of complex natural products, to supramolecular chemistry, and materials science. In this work, a dozen internationally renowned experts and leaders in the field bring the reader up to date by documenting and critically analyzing current developments and uses of metal-catalyzed cross-coupling reactions. A particularly attractive and useful feature, that enhances the practical value of this monograph, is the inclusion of key synthetic protocols, in experimental format, chosen for broad utility and application. This practice-oriented book can offer the practitioner short cuts to ensure they remain up-to-date with the latest developments.
Download or read book Part A written by David Lapointe and published by . This book was released on 2012 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Palladium and Nickel Catalyzed Transformations Forming Functionalized Heterocycles written by Hyung Yoon and published by Springer Nature. This book was released on 2020-09-02 with total page 236 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book presents Pd- and Ni-catalyzed transformations generating functionalized heterocycles. Transition metal catalysis is at the forefront of synthetic organic chemistry since it offers new and powerful methods to forge carbon–carbon bonds in high atom- and step-economy. In Chapter 1, the author describes a Pd- and Ni-catalyzed cycloisomerization of aryl iodides to alkyl iodides, known as carboiodination. In the context of the Pd-catalyzed variant, the chapter explores the production of enantioenriched carboxamides through diastereoselective Pd-catalyzed carboiodination. It then discusses Ni-catalyzed reactions to generate oxindoles and an enantioselective variant employing a dual ligand system. Chapter 2 introduces readers to a Pd-catalyzed diastereoselective anion-capture cascade. It also examines diastereoselective Pd-catalyzed aryl cyanation to synthesize alkyl nitriles, a method that generates high yields of borylated chromans as a single diastereomer, and highlights its synthetic utility. Lastly, Chapter 3 presents a Pd-catalyzed domino process harnessing carbopalladation, C–H activation and π-system insertion (benzynes and alkynes) to generate spirocycles. It also describes the mechanistic studies performed on these reactions.
Download or read book Computational Methods in Organometallic Catalysis written by Yu Lan and published by John Wiley & Sons. This book was released on 2021-03-24 with total page 672 pages. Available in PDF, EPUB and Kindle. Book excerpt: The book includes a historical introduction to organometallic chemistry, a survey of mechanisms, and an extensive introduction to quantum mechanical computational methods.
Download or read book C H Bond Activation and Catalytic Functionalization I written by Pierre H. Dixneuf and published by Springer. This book was released on 2015-12-18 with total page 269 pages. Available in PDF, EPUB and Kindle. Book excerpt: The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics of pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors. All chapters from Topics in Organometallic Chemistry are published OnlineFirst with an individual DOI. In references, Topics in Organometallic Chemistry is abbreviated as Top Organomet Chem and cited as a journal.
Download or read book Heterocyclic N Oxides written by Oleg V. Larionov and published by Springer. This book was released on 2017-07-12 with total page 163 pages. Available in PDF, EPUB and Kindle. Book excerpt: The series Topics in Heterocyclic Chemistry presents critical reviews on present and future trends in the research of heterocyclic compounds. Overall the scope is to cover topics dealing with all areas within heterocyclic chemistry, both experimental and theoretical, of interest to the general heterocyclic chemistry community. The series consists of topic related volumes edited by renowned editors with contributions of experts in the field. All chapters from Topics in Heterocyclic Chemistry are published Online First with an individual DOI. In references, Topics in Heterocyclic Chemistry is abbreviated as Top Heterocycl Chem and cited as a journal.
Download or read book Artificial Metalloenzymes and MetalloDNAzymes in Catalysis written by Montserrat Diéguez and published by John Wiley & Sons. This book was released on 2018-02-21 with total page 431 pages. Available in PDF, EPUB and Kindle. Book excerpt: An important reference for researchers in the field of metal-enzyme hybrid catalysis Artificial Metalloenzymes and MetalloDNAzymes in Catalysis offers a comprehensive review of the most current strategies, developed over recent decades, for the design, synthesis, and optimization of these hybrid catalysts as well as material about their application. The contributors—noted experts in the field—present information on the preparation, characterization, and optimization of artificial metalloenzymes in a timely and authoritative manner. The authors present a thorough examination of this interesting new platform for catalysis that combines the excellent selective recognition/binding properties of enzymes with transition metal catalysts. The text includes information on the various applications of metal-enzyme hybrid catalysts for novel reactions, offers insights into the latest advances in the field, and contains an informative perspective on the future: Explores the development of artificial metalloenzymes, the modern and strongly evolving research field on the verge of industrial application Contains a comprehensive reference to the research area of metal-enzyme hybrid catalysis that has experienced tremendous growth in recent years Includes contributions from leading researchers in the field Shows how this new catalysis combines the selective recognition/binding properties of enzymes with transition metal catalysts Written for catalytic chemists, bioinorganic chemists, biochemists, and organic chemists, Artificial Metalloenzymes and MetalloDNAzymes in Catalysis offers a unique reference to the fundamentals, concepts, applications, and the most recent developments for more efficient and sustainable synthesis.
Download or read book Computational Advances of Rh Catalyzed C H Functionalization written by Yu Lan and published by Springer Nature. This book was released on 2021-02-26 with total page 132 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book offers a comprehensive overview of recent theoretical studies on rhodium-catalyzed C-H functionalization, a topic that has attracted considerable attention over the years. It includes a brief experimental history, elementary reactions, and theoretical perspectives and describes in detail recent advanced computational studies on different types of Rh-catalyzed C-H functionalization, the underlying mechanisms, and the origin of regioselectivity in a series of such reactions. Providing examples shows readers how to use theoretical tools to solve problems related to mechanisms of organometallic reactions. As such, the book is an interesting and useful resource for a wide readership in various fields involving synthetic organic, organometallic, and catalysis reactions.
Download or read book Mechanistic Studies on Transition Metal catalyzed C H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods written by Gui-Juan Cheng and published by . This book was released on 2017 with total page 126 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis presents detailed mechanistic studies on a series of important C-H activation reactions using combined computational methods and mass spectrometry experiments. It also provides guidance on the design and improvement of catalysts and ligands. The reactions investigated include: (i) a nitrile-containing template-assisted meta-selective C-H activation, (ii) Pd/mono-N-protected amino acid (MPAA) catalyzed meta-selective C-H activation, (iii) Pd/MPAA catalyzed asymmetric C-H activation reactions, and (iv) Cu-catalyzed sp3 C-H cross-dehydrogenative-coupling reaction. The book reports on a novel dimeric Pd-M (M = Pd or Ag) model for reaction (i), which successfully explains the meta-selectivity observed experimentally. For reaction (ii), with a combined DFT/MS method, the author successfully reveals the roles of MPAA ligands and a new C-H activation mechanism, which accounts for the improved reactivity and high meta-selectivity and opens new avenues for ligand design. She subsequently applies ion-mobility mass spectrometry to capture and separate the [Pd(MPAA)(substrate)] complex at different stages for the first time, providing support for the internal-base model for reaction (iii). Employing DFT studies, she then establishes a chirality relay model that can be widely applied to MPAA-assisted asymmetric C-H activation reactions. Lastly, for reaction (iv) the author conducts detailed computational studies on several plausible pathways for Cu/O2 and Cu/TBHP systems and finds a reliable method for calculating the single electron transfer (SET) process on the basis of benchmark studies.
Download or read book C H Activation for Asymmetric Synthesis written by Françoise Colobert and published by John Wiley & Sons. This book was released on 2019-11-11 with total page 294 pages. Available in PDF, EPUB and Kindle. Book excerpt: Provides, in one handbook, comprehensive coverage of one of the hottest topics in stereoselective chemistry Written by leading international authors in the field, this book introduces readers to C-H activation in asymmetric synthesis along with all of its facets. It presents stereoselective C-H functionalization with a broad coverage, from outer-sphere to inner-sphere C-H bond activation, and from the control of olefin geometry to the induction of point, planar and axial chirality. Moreover, methods wherein asymmetry is introduced either during the C-H activation or in a different elementary step are discussed. Presented in two parts?asymmetric activation of C(sp3)-H bonds and stereoselective synthesis implying activation of C(sp2)-H bonds?CH-Activation for Asymmetric Synthesis showcases the diversity of stereogenic elements, which can now be constructed by C-H activation methods. Chapters in Part 1 cover: C(sp3)-H bond insertion by metal carbenoids and nitrenoids; stereoselective C-C bond and C-N bond forming reactions through C(sp3)?H bond insertion of metal nitrenoids; enantioselective intra- and intermolecular couplings; and more. Part 2 looks at: C-H activation involved in stereodiscriminant step; planar chirality; diastereoselective formation of alkenes through C(sp2)?H bond activation; amongst other methods. -Covers one of the most rapidly developing fields in organic synthesis and catalysis -Clearly structured in two parts (activation of sp3- and activation of sp2-H bonds) -Edited by two leading experts in C-H activation in asymmetric synthesis CH-Activation for Asymmetric Synthesis will be of high interest to chemists in academia, as well as those in the pharmaceutical and agrochemical industry.
Download or read book The Mizoroki Heck Reaction written by Martin Oestreich and published by John Wiley & Sons. This book was released on 2009-02-11 with total page 608 pages. Available in PDF, EPUB and Kindle. Book excerpt: Exploring the importance of Richard F. Heck’s carbon coupling reaction, this book highlights the subject of the 2010 Nobel Prize in Chemistry for palladium-catalyzed cross couplings in organic synthesis, and includes a foreword from Nobel Prize winner Richard F. Heck. The Mizoroki-Heck reaction is a palladium-catalyzed carbon–carbon bond forming process which is widely used in organic and organometallic synthesis. It has seen increasing use in the past decade as chemists look for strategies enabling the controlled construction of complex carbon skeletons. The Mizoroki-Heck Reaction is the first dedicated volume on this important reaction, including topics on: mechanisms of the Mizoroki-Heck reaction intermolecular Mizoroki-Heck reactions focus on regioselectivity and product outcome in organic synthesis waste-minimized Mizoroki-Heck reactions intramolecular Mizoroki-Heck reactions formation of heterocycles chelation-controlled Mizoroki-Heck reactions the Mizoroki-Heck reaction in domino processes oxidative heck-type reactions (Fujiwara-Moritani reactions) Mizoroki-Heck reactions with metals other than palladium ligand design for intermolecular asymmetric Mizoroki-Heck reactions intramolecular enantioselective Mizoroki-Heck reactions desymmetrizing Mizoroki-Heck reactions applications in combinatorial and solid phase syntheses, and the development of modern solvent systems and reaction techniques the asymmetric intramolecular Mizoroki-Heck reaction in natural product total synthesis Several chapters are devoted to asymmetric Heck reactions with particular focus on the construction of otherwise difficult-to-obtain sterically congested tertiary and quaternary carbons. Industrial and academic applications are highlighted in the final section. The Mizoroki-Heck Reaction will find a place on the bookshelves of any organic or organometallic chemist. “I am convinced that this book will rapidly become the most important reference text for research chemists in academia and industry who seek orientation in the rapidly growing and – for the layman – confusing field described as the “’Mizoroki–Heck reaction’.” (Synthesis, March 2010)
Download or read book Applied Organic Chemistry written by Surya K. De and published by John Wiley & Sons. This book was released on 2021-03-08 with total page 856 pages. Available in PDF, EPUB and Kindle. Book excerpt: An indispensable guide for all synthetic chemists who want to learn about the most relevant reactions and reagents employed to synthesize important heterocycles and drugs! The synthesis of natural products, bioactive compounds, pharmaceuticals, and drugs is of fundamental interest in modern organic chemistry. New reagents and reaction methods towards these molecules are being constantly developed. By understanding the mechanisms involved and scope and limitations of each reaction applied, organic chemists can further improve existing reaction protocols and develop novel efficient synthetic routes towards frequently used drugs, such as Aspirin or Penicillin. Applied Organic Chemistry provides a summary of important (name) reactions and reagents applied in modern organic chemistry and drug synthesis. It covers rearrangement, condensation, olefination, metathesis, aromatic electrophilic substitutions, Pd-catalyzed C-C bond forming reactions, multi-component reactions, as well as oxidations and reductions. Each chapter is clearly structured, providing valuable information on reaction details, step-by-step mechanism, experimental procedures, applications, and (patent) references. By providing mechanistic information and representative experimental procedures, this book is an indispensable guide for researchers and professionals in organic chemistry, natural product synthesis, pharmaceutical, and medicinal chemistry, as well as post-graduates preparing themselves for a job in the pharmaceutical industry. Hot Topic: Reviews important classes of organic reactions (incl. name reactions) and reagents in medicinal chemistry. Useful: Provides information on reaction details, common reagents, and functional group transformations used to synthesize natural products, bioactive compounds, drugs, and pharmaceuticals, e.g. Aspirin, Penicillin. Unique: For every reaction the mechanism is explained step by step, and representative experimental procedures are given, unlike most books in this area. User-friendly: Chapters are clearly structured making it easy for the reader to compare different reactions. Applied Organic Chemistry is an indispensable guide for researchers and professionals in organic chemistry, natural product synthesis, pharmaceutical, and medicinal chemistry, as well as post-graduates preparing themselves for a job in the pharmaceutical industry.
Download or read book Understanding Organometallic Reaction Mechanisms and Catalysis written by Valentin P. Ananikov and published by John Wiley & Sons. This book was released on 2014-08-29 with total page 483 pages. Available in PDF, EPUB and Kindle. Book excerpt: Exploring and highlighting the new horizons in the studies of reaction mechanisms that open joint application of experimental studies and theoretical calculations is the goal of this book. The latest insights and developments in the mechanistic studies of organometallic reactions and catalytic processes are presented and reviewed. The book adopts a unique approach, exemplifying how to use experiments, spectroscopy measurements, and computational methods to reveal reaction pathways and molecular structures of catalysts, rather than concentrating solely on one discipline. The result is a deeper understanding of the underlying reaction mechanism and correlation between molecular structure and reactivity. The contributions represent a wealth of first-hand information from renowned experts working in these disciplines, covering such topics as activation of small molecules, C-C and C-Heteroatom bonds formation, cross-coupling reactions, carbon dioxide converison, homogeneous and heterogeneous transition metal catalysis and metal-graphene systems. With the knowledge gained, the reader will be able to improve existing reaction protocols and rationally design more efficient catalysts or selective reactions. An indispensable source of information for synthetic, analytical, and theoretical chemists in academia and industry.
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 Organic Reaction Mechanisms 2017 written by A. C. Knipe and published by John Wiley & Sons. This book was released on 2020-07-20 with total page 672 pages. Available in PDF, EPUB and Kindle. Book excerpt: Organic Reaction Mechanisms 2017, the 53rd annual volume in this highly successful and unique series, surveys research on organic reaction mechanisms described in the available literature dated 2017. The following classes of organic reaction mechanisms are comprehensively reviewed: • Reaction of Aldehydes and Ketones and their Derivatives • Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and their Derivatives • Oxidation and Reduction • Carbenes and Nitrenes • Nucleophilic Aromatic Substitution • Electrophilic Aromatic Substitution • Carbocations • Nucleophilic Aliphatic Substitution • Carbanions and Electrophilic Aliphatic Substitution • Elimination Reactions • Polar Addition Reactions • Cycloaddition Reactions • Molecular Rearrangements An experienced team of authors compile these reviews every year, so that the reader can rely on a continuing quality of selection and presentation.
