Download or read book Development and Applications of Copper I Hydride Catalysis in Asymmetric Reactions and Heterocycle Synthesis written by Yujing Zhou (Ph. D.) and published by . This book was released on 2021 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Chapter 2. Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates The direct asymmetric copper hydride (CuH)-catalyzed coupling of [alpha],[beta]-unsaturated carboxylic acids to aryl alkenes is developed to access chiral [alpha]-aryl dialkyl ketones. A variety of substrate substitution patterns, sensitive functional groups and heterocycles are tolerated in this reaction, which significantly expands the range of accessible products compared to existing hydroacylation methodology. Although mechanistic studies are ongoing, we propose that CuH-catalyzed silylation of unsaturated acids occurs to access a uniquely effective acyl electrophilic coupling partner. Chapter 3. CuH-Catalyzed Asymmetric Reduction of [alpha],[beta]-Unsaturated Carboxylic Acids to [beta]-Chiral Aldehydes The copper hydride (CuH)-catalyzed enantioselective reduction of [alpha],[beta]-unsaturated carboxylic acids to saturated aldehydes is reported. This protocol provides a new method to access a variety of [beta]-chiral aldehydes in good yields, with high levels of enantioselectivity and broad functional group tolerance. A reaction pathway involving a ketene intermediate is proposed based on preliminary mechanistic studies and density functional theory calculations. Chapter 4. CuH-Catalyzed Asymmetric Reductive Amidation of [alpha],[beta]-Unsaturated Carboxylic Acids The direct enantioselective copper hydride (CuH)-catalyzed synthesis of [beta]-chiral amides from [alpha],[beta]-unsaturated carboxylic acids and secondary amines under mild reaction conditions is reported. The method utilizes readily accessible carboxylic acids, and tolerates a variety of functional groups at [beta]-position including several heteroarenes. A subsequent iridium-catalyzed reduction to [gamma]-chiral amines can be performed in the same flask without purification of the intermediate amides. Chapter 5. CuH-Catalyzed Asymmetric Hydroamidation of Vinylarenes A CuH-catalyzed enantioselective hydroamidation reaction of vinylarenes has been developed using readily accessible 1,4,2-dioxazol-5-ones as electrophilic amidating reagents. This method provides a straightforward and efficient approach to synthesize chiral amides in good yields with high levels of enantiopurity under mild conditions. Moreover, this transformation tolerates substrates bearing a broad range of functional groups. Chapter 6. Enantioselective Allylation Using Allene, a Petroleum Cracking Byproduct Allene (C3H4) gas is produced and separated on million-metric-ton scale per year during petroleum refining but is rarely employed in organic synthesis. Meanwhile, the addition of an allyl group (C3H5) to ketones is among the most common and prototypical reactions in synthetic chemistry. Herein, we report that the combination of allene gas with inexpensive and environmentally benign hydrosilanes, such as PMHS, can serve as a replacement for stoichiometric quantities of allylmetal reagents, which are required in most enantioselective ketone allylation reactions. This process is catalyzed by copper catalyst and commercially available ligands, operates without specialized equipment or pressurization, and tolerates a broad range of functional groups. Furthermore, the exceptional chemoselectivity of this catalyst system enables industrially relevant C3 hydrocarbon mixtures of allene with methylacetylene and propylene to be applied directly. Based on our strategy, we anticipate the rapid development of methods that leverage this unexploited feedstock as an allyl anion surrogate. Chapter 7. Synthesis of Pyrroles through the CuH-Catalyzed Coupling of Enynes and Nitriles Herein, we describe an efficient method to prepare polysubstituted pyrroles via a copper-hydride (CuH)- catalyzed enyne-nitrile coupling reaction. This protocol accommodates both aromatic and aliphatic substituents and a broad range of functional groups, providing a variety of N-H pyrroles in good yields and with high regioselectivity. We propose that the Cu-based catalyst promotes both the initial reductive coupling and subsequent cyclization steps. Density functional theory (DFT) calculations were performed to help elucidate the reaction mechanism.
Download or read book Copper Catalysis in Organic Synthesis written by Gopinathan Anilkumar and published by John Wiley & Sons. This book was released on 2020-12-07 with total page 504 pages. Available in PDF, EPUB and Kindle. Book excerpt: The most current information on growing field of copper catalysis Copper Catalysis in Organic Synthesis contains an up-to-date overview of the most important reactions in the presence of copper catalysts. The contributors—noted experts on the topic—provide an introduction to the field of copper catalysis, reviewing its development, scope, and limitations, as well as providing descriptions of various homo- and cross-coupling reactions. In addition, information is presented on copper-catalyzed C–H activation, amination, carbonylation, trifluoromethylation, cyanation, and click reactions. Comprehensive in scope, the book also describes microwave-assisted and multi-component transformations as well as copper-catalyzed reactions in green solvents and continuous flow reactors. The authors highlight the application of copper catalysis in asymmetric synthesis and total synthesis of natural products and heterocycles as well as nanocatalysis. This important book: Examines copper and its use in organic synthesis as a more cost-effective and sustainable for researchers in academia and industry Offers the first up-to-date book to explore copper as a first line catalyst for many organic reactions Presents the most significant developments in the area, including cross-coupling reactions, C–H activation, asymmetric synthesis, and total synthesis of natural products and heterocycles Contains over 20 contributions from leaders in the field Written for catalytic chemists, organic chemists, natural products chemists, pharmaceutical chemists, and chemists in industry, Copper Catalysis in Organic Synthesis offers a book on the growing field of copper catalysis, covering cross-coupling reactions, C–H activation, and applications in the total synthesis of natural products.
Download or read book Copper Catalyzed Asymmetric Synthesis written by Alexandre Alexakis and published by John Wiley & Sons. This book was released on 2013-12-30 with total page 467 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book reflects the increasing interest among the chemical synthetic community in the area of asymmetric copper-catalyzed reactions, and introduces readers to the latest, most significant developments in the field. The contents are organized according to reaction type and cover mechanistic and spectroscopic aspects as well as applications in the synthesis of natural products. A whole chapter is devoted to understanding how primary organometallics interact with copper to provide selective catalysts for allylic substitution and conjugate addition, both of which are treated in separate chapters. Another is devoted to the variety of substrates and experimental protocols, while an entire chapter covers the use on non-carbon nucleophiles. Other chapters deal with less-known reactions, such as carbometallation or the additions to imines and related systems, while the more established reactions cyclopropanation and aziridination as well as the use of copper (II) Lewis acids are warranted their own special chapters. Two further chapters concern the processes involved, as determined by mechanistic studies. Finally, a whole chapter is devoted to the synthetic applications. This is essential reading for researchers at academic institutions and professionals at pharmaceutical or agrochemical companies.
Download or read book New Fundamental Transformations of Heterocyclic Compounds Enabled by Copper Catalysis written by Michael William Gribble (Jr.) and published by . This book was released on 2020 with total page 320 pages. Available in PDF, EPUB and Kindle. Book excerpt: Chapter One. Introduction to Catalytic C–C−Bond−Forming Reactions of Alkylcopper(I) Nucleophiles This chapter provides a brief historical perspective on the development of Cucatalyzed C–C−bond-forming reactions and an overview of the general facets of organocopper reactivity that are most important to the work documented in subsequent chapters. Chapter Two: Asymmetric Copper-Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles Copper hydride complexes catalyze highly enantioselective Markovnikov hydrosilylation of vinylarenes and vinyl heterocycles. This method has a broad scope and enables both the synthesis of isolable silanes and the conversion of crude products to chiral alcohols. DFT calculations support a mechanism proceeding by hydrocupration followed by !-bond metathesis with a hydrosilane. Chapter Three: Asymmetric Cu-Catalyzed 1,4−Dearomatization of Pyridines and Pyridazines without Preactivation of the Heterocycle or Nucleophile. A chiral copper hydride complex catalyzes C-C bond-forming dearomatization of pyridines and pyridazines at room temperature. The catalytic reaction operates directly on free heterocycles and generates the nucleophiles in situ, eliminating the need for stoichiometric preactivation of either reaction partner; further, it is one of very few methods available for the enantioselective 1,4−dearomatization of heteroarenes. Combining the dearomatization with facile derivatization steps enables one-pot syntheses of enantioenriched pyridines and piperidines. Chapter Four: Evidence for Simultaneous Dearomatization of Two Arenes Under Mild Conditions in Cu(I)-Catalyzed Direct Asymmetric Dearomatization of Pyridine Bis(phosphine) copper hydride complexes are uniquely able to catalyze the direct dearomatization of unactivated pyridines with carbon nucleophiles, but the mechanistic basis for this result has been unclear. Here we show that, contrary to our initial hypotheses, the catalytic mechanism is monometallic and proceeds via dearomative rearrangement of the phenethylcopper nucleophile to a Cparametalated form prior to reaction at heterocycle C4. Our studies support an unexpected heterocycle-promoted pathway for this net 1,5−Cu−migration beginning with a doubly dearomative imidoyl-Cu-ene reaction. Kinetics, substituent effects, computational modeling, and spectroscopic studies support the involvement of this unusual process. The CuL2 fragment subsequently mediates a stepwise Cope rearrangement of the doubly dearomatized intermediate to give the C4− functionalized 1,4-dihydropyridine, lowering a second barrier in the pathway that otherwise prohibit efficient asymmetric catalysis.
Download or read book Copper in N Heterocyclic Chemistry written by Ananya Srivastava and published by Elsevier. This book was released on 2020-11-13 with total page 506 pages. Available in PDF, EPUB and Kindle. Book excerpt: Copper in N-Heterocyclic Chemistry provides an overview of copper-catalyzed synthesis and functionalization of N-heterocyclic compounds, covering all recent developments in a way that is ideal for researchers and students working in the area of synthetic organic chemistry and medicinal chemistry. The book explores N-heterocyclic compounds as unique structural units in the development of natural products and pharmaceuticals, along with the remarkable progress made in the area of high atom economic strategies, and more recently, copper-catalyzed C-H activation and its applications in organic synthesis. Readers will find troubleshooting protocols, as well as the advantages and limitations of each method discussed. As copper catalysts show versatile chemical reactivity in many aspects, including their oxidation states 0–3 are accessible and their ability to facilitate bond formations due to their ability to serve as Lewis acids, oxidizing agents and catalysts, this book is an ideal resource on the topics explored. Discusses novel synthetic methods developed over the past decade for copper-catalyzed synthesis of N-heterocyclic compounds Covers the most recent methodologies adapted in synthetic chemistry for applications in natural products and pharmaceuticals Includes troubleshooting protocols, as well as the advantages and limitations of each method discussed in detail
Download or read book New Trends in Asymmetric Catalysis written by Giorgio Della Sala and published by MDPI. This book was released on 2021-08-30 with total page 172 pages. Available in PDF, EPUB and Kindle. Book excerpt: The synthesis of enantiopure organic compounds is a key issue for several applications in pharmacology, food chemistry, agricultural chemistry, perfumery, materials science and other industrial sectors. Nowadays, asymmetric catalysis is undoubtedly the most important tool to achieve this goal. This technology, in fact, enables the production of large amounts of enantiomerically enriched compounds, employing relatively small quantities of chiral enantiopure catalysts, which is exactly what is accomplished by enzymes in nature. Since the pioneering works of Noyori, Knowles and Sharpless, which later earned them the Nobel Prize in Chemistry, asymmetric catalysis has experienced a rapid and relentless development in the last fifty years. The tremendous expansion of enantioselective transformations, the design of novel and more efficient organometallic and organic catalysts, the development of sophisticated bioreactors and cell factories, are just some of the elements responsible for such growth. However, new challenges of asymmetric catalysis are devoted to enhancing the process’s sustainability, by the introduction of recyclable and low-cost catalysts, and the use of renewable starting materials and energy source. This book provides an overview of some of these development directions and comprises a collection of review papers and a research article authored by renowned researchers actively involved in this field. The topics covered by the review papers are photoredox-catalyzed reactions of imines, asymmetric catalytic electrosynthesis, cooperative catalysis of chiral N-heterocyclic carbenes and Lewis acid, and asymmetric ring-opening reactions of epoxides catalyzed by metal–salen complexes. The research article presents a proline-catalyzed aldol reaction in water–methanol solvent mixture.
Download or read book Copper Mediated Cross Coupling Reactions written by Gwilherm Evano and published by John Wiley & Sons. This book was released on 2013-09-23 with total page 682 pages. Available in PDF, EPUB and Kindle. Book excerpt: Providing comprehensive insight into the use of copper in cross-coupling reactions, Copper-Mediated Cross-Coupling Reactions provides a complete up-to-date collection of the available reactions and catalytic systems for the formation of carbon-heteroatom and carbon-carbon bonds. This essential reference covers a broad scope of copper-mediated reactions, their variations, key advances, improvements, and an array of academic and industrial applications that have revolutionized the field of organic synthesis. The text also discusses the mechanism of these transformations, the use of copper as cost-efficient alternative to palladium, as well as recently developed methods for conducting copper-mediated reactions with supported catalysts.
Download or read book Copper Catalyzed Multi Component Reactions written by Yusuke Ohta and published by Springer Science & Business Media. This book was released on 2011-01-20 with total page 110 pages. Available in PDF, EPUB and Kindle. Book excerpt: A copper-catalyzed direct synthesis of 2-(aminomethyl)indoles by catalytic domino reaction including multi-component coupling was developed, and is the first example of a three-component indole formation without producing salts as a byproduct. Based on this reaction, a copper-catalyzed synthesis of 3-(aminomethyl)isoquinoline was accomplished which represents an unprecedented isoquinoline synthesis through a four-component coupling reaction. Following these results, extensive application studies using one-pot palladium-, acid-, or base-promoted cyclization revealed that indole- or isoquinoline-fused polycyclic compounds can be readily synthesized through multi-component reactions. As the concept of Green Chemistry becomes ever more important, these findings may provide efficient and atom-economical approaches to the diversity-oriented synthesis of bioactive compounds containing a complex structure. This could lead to development of promising drug leads with structural complexity. The work of this thesis will go on to inspire the synthetic research of many readers.
Download or read book Noble Metal Noble Value Ru Rh Pd catalyzed Heterocycle Synthesis written by Xiao-feng Wu and published by World Scientific. This book was released on 2016-06-24 with total page 390 pages. Available in PDF, EPUB and Kindle. Book excerpt: Heterocyclic chemistry constitutes the largest branch of chemistry, covering almost two-thirds of literature in the field. In addition, around 90% of naturally-occurring molecules have heterocycles as their core structure. Therefore, as a central part of organic chemistry, the discovery of new methodologies in synthesizing heterocyclic compounds is essential to their continued application and development. Transition metal catalysts offer a low cost and often low toxicity pathway for heterocycles synthesis, while the use of noble metals represents an alternative form of experimentation which is discussed in the book.Noble Metals, Noble Value provides the first comprehensive analysis of the applications of the noble metals of ruthenium (Ru), rhodium (Rh) and palladium (Pd) catalysts in heterocycles synthesis. Pairs of chapters are dedicated to summarizing each of the metals when applied to either five- or six-membered heterocyclic syntheses. An introduction to the importance of heterocycles and possible procedures for the preparation of heterocyclic compounds is also given.With up to date research and findings, this review is excellently suited to academics and professionals in the field of chemistry, with a particular focus on the specialities of biological, catalytic and organic chemistry.
Download or read book Economic Synthesis of Heterocycles written by Xiao-Feng Wu and published by Royal Society of Chemistry. This book was released on 2014-05-21 with total page 335 pages. Available in PDF, EPUB and Kindle. Book excerpt: Heterocycle synthesis is one of the largest areas of modern organic chemistry. Heterocycles have a broad range of applications including pharmaceuticals, agrochemicals and dyes, and are the core structure to around 90% of naturally-occurring molecules. Transition metal catalysts have become favoured in heterocycle synthesis, not least because of their low cost, but also due to their relatively low environmental toxicity and biocompatibility. This book presents an overview of the state-of-the-art in transition metal catalysis for heterocycle synthesis. Each metal is discussed in turn, presenting a comprehensive source of information on the use of zinc, iron, copper, cobalt, manganese, and nickel in a sustainable and economic manner. Referencing the latest primary literature, and authored by active researchers in the field, this book is a must-have resource for anyone wishing to undertake an economic and sustainable approach to heterocycle synthesis.
Download or read book Transition Metal Catalyzed Heterocycle Synthesis via C H Activation written by Xiao-Feng Wu and published by John Wiley & Sons. This book was released on 2016-03-07 with total page 596 pages. Available in PDF, EPUB and Kindle. Book excerpt: Reflecting the tremendous growth of this hot topic in recent years, this book covers C-H activation with a focus on heterocycle synthesis. As such, the text provides general mechanistic aspects and gives a comprehensive overview of catalytic reactions in the presence of palladium, rhodium, ruthenium, copper, iron, cobalt, and iridium. The chapters are organized according to the transition metal used and sub-divided by type of heterocycle formed to enable quick access to the synthetic route needed. Chapters on carbonylative synthesis of heterocycles and the application of C-H activation methodology to the synthesis of natural products are also included. Written by an outstanding team of authors, this is a valuable reference for researchers in academia and industry working in the field of organic synthesis, catalysis, natural product synthesis, pharmaceutical chemistry, and crop protection.
Download or read book Development of Copper I Hydride catalyzed Asymmetric Olefin Hydrofunctionalization Reactions written by Sheng Feng (Scientist in chemistry) and published by . This book was released on 2022 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: The work described in this dissertation focuses on developing copper(I) hydride (CuH)-catalyzed enantioselective hydrofunctionalization reactions of olefins. The first chapter highlights a method on CuH-catalyzed asymmetric hydroamination of strained trisubstituted alkenes, including cyclobutenes and cyclopropenes. The second chapter presents an approach for accessing enantioenriched [alpha]-quaternary carboxylic acids, through CuH-catalyzed hydrocarboxylation of allenes. The third chapter demonstrates the enantioselective hydrocarbamoylation of alkenes enable by dual CuH and Pd catalysis.
Download or read book Synthesis of Heterocycles via Metal Catalyzed Reactions that Generate One or More Carbon Heteroatom Bonds written by John P. Wolfe and published by Springer. This book was released on 2013-09-11 with total page 276 pages. Available in PDF, EPUB and Kindle. Book excerpt: Synthesis of Saturated Heterocycles via Metal-Catalyzed Alkene Carboamination or Carboalkoxylation Reactions, by John P. Wolfe Synthesis of Saturated Heterocycles via Metal-Catalyzed Alkene Diamination, Aminoalkoxylation, or Dialkoxylation Reactions, by Sherry R. Chemler Synthesis of Heterocycles via Metal-Catalyzed Wacker-Type Oxidative Cyclization Reactions of Alkoxy- or Amino-Alkenes, by Wanbin Zhang Synthesis of Saturated Heterocycles via Metal-Catalyzed Hydroamination or Hydroalkoxylation Reactions, by Lisa D. Julian Synthesis of Saturated Heterocycles via Metal-Catalyzed Allylic Alkylation Reactions, by Aaron Aponick Synthesis of Heterocycles via Metal-Catalyzed Cascade/Domino Reactions that Generate a C–N or C–O Bond, by Mark Lautens Synthesis of Saturated Heterocycles via Metal-Catalyzed Formal Cycloaddition Reactions that Generate a C–N or C–O Bond, by Jerome Waser
Download or read book Heterocycles from Double Functionalized Arenes written by Xiao-Feng Wu and published by Royal Society of Chemistry. This book was released on 2015 with total page 315 pages. Available in PDF, EPUB and Kindle. Book excerpt: An introduction to transition metal catalyzed coupling reactions of double-functionalized arenes in heterocycle synthesis.
Download or read book Catalytic Asymmetric Synthesis written by Takahiko Akiyama and published by John Wiley & Sons. This book was released on 2022-05-27 with total page 798 pages. Available in PDF, EPUB and Kindle. Book excerpt: Catalytic Asymmetric Synthesis Seminal text presenting detailed accounts of the most important catalytic asymmetric reactions known today This book covers the preparation of enantiomerically pure or enriched chemical compounds by use of chiral catalyst molecules. While reviewing the most important catalytic methods for asymmetric organic synthesis, this book highlights the most important and recent developments in catalytic asymmetric synthesis. Edited by two well-qualified experts, sample topics covered in the work include: Metal catalysis, organocatalysis, photoredox catalysis, enzyme catalysis C–H bond functionalization reactions Carbon–carbon bond formation reactions, carbon–halogen bond formation reactions, hydrogenations, polymerizations, flow reactions Axially chiral compounds Retaining the best of its predecessors but now thoroughly up to date with the important and recent developments in catalytic asymmetric synthesis, the 4th edition of Catalytic Asymmetric Synthesis serves as an excellent desktop reference and text for researchers and students, from upper-level undergraduates all the way to experienced professionals in industry or academia.
Download or read book Mechanistic Studies and Applications of the Copper catalyzed Rearrangement of Vinyl Heterocycles written by Daniel James Mack and published by . This book was released on 2013 with total page 890 pages. Available in PDF, EPUB and Kindle. Book excerpt: The development of new synthetic methods advances the study of chemistry on many fronts, including new drugs for the treatment of human disease and new materials. The copper-catalyzed rearrangement of vinyl heterocycles is one such method, providing access to a wide array of five-membered oxygen, nitrogen, and sulfur-containing heterocycles. To harness the true potential of a new methodology, an understanding of the mechanistic underpinnings is required. Utilizing an array of mechanistic tools, the rearrangement of vinyl aziridines is studied in detail. Using mechanistically inspired metal additives, a dramatic acceleration of the rearrangement of vinyl aziridines was realized. Demonstrating the use of in situ reducing agents significantly accelerate the rearrangement, suggesting a copper(I) species is the active catalytic species. This was corroborated through the use of (COD)Cu(hfacac) as a copper(I) starting point. Detailed NMR kinetic studies revealed the relative importance of olefin and sulfonamide electronics, and that the rearrangement is first order in substrate and first order in catalyst. As a result, a new catalytic system was discovered, which provides enhanced chemoselectivity and milder reaction conditions towards five-membered heterocycles. In addition, studying the mechanism provided a new direction for future rational catalyst designs towards more active catalysts, and catalysts for chiral applications, such as asymmetric desymmetrization. To further demonstrate the utility of the new copper(I) catalytic system, an expedient and scalable approach was designed utilizing (COD)Cu(hfacac) in the first total synthesis of members of a family of heterocyclic labdane natural products. Through synthesis, conformation and clarification of the structural assignment of isolated smallmolecules was realized. The route provided access to quantities of material for biological screening purposes, and the versatility of the route could be used to provide synthetic analogues of the natural structures.
Download or read book Heterogeneous Catalysis written by K.L. Ameta, Ph.D. and published by CRC Press. This book was released on 2014-09-13 with total page 360 pages. Available in PDF, EPUB and Kindle. Book excerpt: For more than a century, bioactive heterocycles have formed one of the largest areas of research in organic chemistry. They are important from a biological and industrial point of view as well as to the understanding of life processes and efforts to improve the quality of life. Heterogeneous Catalysis: A Versatile Tool for the Synthesis of Bioactive Heterocycles highlights the recent methodologies used in the synthesis of such bioactive systems and focuses on the role of heterogeneous catalysis in the design and synthesis of various biologically active heterocyclic compounds of pharmacological interest. Topics include: Synthetic protocols for the construction of heterocyclic systems employing silica-bound catalysts Recent advances in heterogeneous copper-catalyzed reactions for the synthesis of bioactive heterocycles Features of silica-based heterogeneous catalysts, such as abundance, ease of use, and stability Ultrasound as an effective tool for accelerating reactions Organic transformations catalyzed by nano-ZnO as a valuable heterogeneous catalyst Heterogeneous catalysts employed in the synthesis of coumarins Heterocyclizations in the presence of silver salts Home-made organometallic silica sources, known as silatranes Reflecting the focused studies currently conducted in these areas, the book also examines anticancer, antifungal, antibacterial, anti-HIV, anti-inflammatory, antioxidant, and many more biological activities of heterocyclic compounds. It is essential reading for postgraduate and research scholars in the fields of biochemistry, chemical biology, medicinal chemistry and pharmaceutical chemistry.
