Download or read book Methods and Strategies for C N Bond Formation Reactions written by Zahra Taherinia and published by Royal Society of Chemistry. This book was released on 2023-12-15 with total page 334 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Methods and Strategies for C N Bond Formation Reactions written by Zahra Taherinia and published by Royal Society of Chemistry. This book was released on 2023-12-15 with total page 388 pages. Available in PDF, EPUB and Kindle. Book excerpt: Organic compounds containing amino groups are one of the most important classes of chemicals in both academia and industry. This class of materials is a very important structural motif in organic synthesis due to its widespread applications in natural products, agrochemicals, pharmaceuticals, and advanced materials. This book is a concise overview of modern approaches to N-alkylation and N-arylation of primary, secondary and tertiary amines using alkylating and arylating reagents with amino sources found in both basic and applied chemical research. The work also discusses key examples of amine synthesis from a sustainable perspective, using deep eutectic solvents and the application of amines in different areas. It is an ideal reference for advanced and postgraduate students as well as academic and industrial chemists working in organic, natural product, catalytic, medicinal, and polymer chemistry.

Download or read book Amination and Formation of sp2 C N Bonds written by Marc Taillefer and published by Springer. This book was released on 2013-12-12 with total page 233 pages. Available in PDF, EPUB and Kindle. Book excerpt: Palladium-Catalyzed sp2C–N Bond Forming Reactions: Recent Developments and Applications. Metal-catalyzed C(sp2)-N bond formation.- Recent Developments in Recyclable Copper Catalyst Systems for C−N Bond Forming Cross-Coupling Reactions Using Aryl Halides and Arylboronic Acids. Assembly of N-containing heterocycles via Pd and Cu-catalyzed C-N bond formation reactions. Copper-Catalyzed C(aryl)-N Bond Formation.

Download or read book Copper Catalyzed Domino C N Bond Formation for Synthesis of N Containing Compounds Benzimidazoles Imidazoles and Guanidines Approach Toward Total Synthesis of Natural Product Raputindoles written by Jihui Li and published by . This book was released on 2013 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis consists in three parts: bibliographic background, copper-catalyzed reactions for synthesis of N-containing compounds, approach to the synthesis of raputindoles.The first part introduces the domino reactions and their applications, then, copper-mediated reactions for construction of C-N bond formation are reviewed including Ullmann, Goldberg and Chan-Lam coupling, oxidative C-H activation/C-N formation, insertion of nitrenes and carbenoids, and hydroamination of multi-C-C bonds. This can be used as guides to design domino reaction. Following these copper-mediated single C-N bond formation reactions, recent developments of copper-catalyzed domino reactions for synthesis of heterocycles are described.The second part can be divided into three sections: 1) synthesis of benzimidazoles, 2) synthesis of imidazoles and 3) synthesis of guanidines. Each section summarizes the existing methods used for their synthesis. Following it, our synthetic work involving copper-catalyzed C-N bond formation domino reactions is discussed in detail. Our objectives include the synthesis of benzimidazoles through copper-catalyzed sequential reaction of benzamidines and boronic acids, synthesis of imidazoles via copper-catalyzed domino reaction of benzamidines and acetylenes, and synthesis of guanidines and 2-aminobenzimidazoles by Cu-catalyzed three-component reaction of cyanamides, boronic acids and amines. These copper-catalyzed domino reactions show high efficiencies from readily available and simple starting materials.The last part is about the total synthesis of raputindoles. The structure and bioactivities of raputindoles and key reactions for the total synthesis of raputindoles are introduced first, the synthetic strategies are then proposed on basis of relative synthetic methods. The key reactions we use for the synthesis of raputindoles are iridium catalyzed [3+2] annulation of o-formylarylboronic acids and 1,3-dienes, Leimgruber-Batcho indole synthesis, transition-metal catalyzed SN2 substitution and alkylborylation-protondeborylation. According to the three strategies we proposed, lots of relative reactions were investigated. The results show that it is possible to synthesize the raputindole molecules based on the iridium catalyzed [3+2] annulation of 2-formylarylboronic acids and 1,3-dienes.

Download or read book Carbon carbon Bond Formation written by Robert L. Augustine and published by CRC Press. This book was released on 1979-04-01 with total page 480 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Advances in the Stille Reaction and New Methods for Continuous Flow Pd catalyzed C N Bond Forming Reactions written by John Robert Naber and published by . This book was released on 2010 with total page 241 pages. Available in PDF, EPUB and Kindle. Book excerpt: Chapter 1: A highly active catalyst system based upon a biaryl monophosphine ligand, XPhos, for the palladium-catalyzed Stille reaction has been developed. This method allows for the coupling of aryl chlorides with a range of tributylarylstannanes to produce the corresponding biaryl compounds in good to excellent yields (61-98%) in short reaction times (4 h). Palladium(II) acetate [Pd(OAc)2] and XPhos in a 1:1.1 ratio were milled into a fine powder that was used as pre-catalyst for these reactions. Chapter 2: A catalyst system for the Stille cross-coupling reactions of aryl mesylates and tosylates is reported. Using the combination of Pd(OAc)2, XPhos, and CsF in t-BuOH an array of aryl and heteroaryl sulfonates were successfully employed in these reactions. Morever, heteroarylstannanes, such as furyl, thienyl, and N-methylpyrrolyl, which are often prone to decomposition, were efficiently coupled under these conditions. Ortho-substitution on the stannane coupling partner was well tolerated; however, the presence of ortho substituents on the aryl sulfonates greatly reduced the efficiency of these reactions. Chapter 3: A continuous-flow, multistep Heck synthesis was made possible by integrating microreactors, liquid-liquid extraction, and microfluidic distillation. The microfluidic distillation enabled solvent exchange from CH2Cl2 in the first reaction step to N, N-dimethylformamide (DMF) in the final reaction step. Chapter 4: A method to mitigate clogging of microsystems during Pd-catalyzed C-N bond-forming reactions under continuous flow conditions was developed. Bridging of particles across the channel and deposition of materials on the walls of the microreactor were both found to be causes that led to clogging and techniques to minimize their effects using sonication were developed. This system allows Pd-catalyzed amination reactions for the formation of a diaryl amines to proceed for extended periods of time without significant pressure increase in the reactor. Chapter 5: A highly efficient method for the Pd-catalyzed coupling of aryl chloride and anilines has been developed. Catalysts based on allyl palladium chloride dimer and BrettPhos, using biphasic reaction conditions of toluene and water with KOH as a base, provided excellent yields for these reactions. The use of a packed bed reactor allowed for these reactions to be run in a continuous flow manner.

Download or read book Methods for C C and C N Bond Formation Via Metallaphotoredox Catalysis written by Robert Wesley Pipal and published by . This book was released on 2021 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: In the field of synthetic organic chemistry, photocatalysis has emerged as a powerful visible light-driven platform for enabling the synthesis of complex molecular scaffolds. These molecules have a wide variety of important applications, spanning pharmaceuticals, agrochemicals, fragrances, and polymers. Through the merger of photoredox and transition metal catalysis, our group has shown over the last decade that numerous attractive bond disconnections can be accessed via photocatalytic generation of alkyl radicals and activated transition metal catalysts. Moreover, due to the facile nature of visible-light activation and its unique reactivity, metallaphotoredox catalysis has witnessed broad utility in radiochemical and biological applications, among others.Described herein are methods and applications of this metallaphotoredox platform. The second chapter of this thesis details a collaboration with Merck and the University of Pennsylvania for the development of a metallaphotoredox-catalyzed radiolabeling strategy. This unified and general approach allows for the installation of (radio)isotope-bearing methyl groups for applications in PET radioligand discovery. In the third chapter, a dual copper photoredox-catalyzed deoxygenative amination strategy is disclosed, effectively harnessing native and abundant alcohols as diverse alkylating reagents for C(sp3)-N bond formation. Chapter four outlines the ongoing collaboration with Janssen, delineating the late-stage peptide functionalization of alcohol-containing amino acid residues via deoxygenative C-C bond formation. Lastly, following a serendipitous discovery from the study detailed in chapter four, a mild and weakly basic dual nickel photoredox-catalyzed arylation of N-heterocycles was examined and is described in chapter five.

Download or read book Remote C H Bond Functionalizations written by Debabrata Maiti and published by John Wiley & Sons. This book was released on 2021-01-05 with total page 448 pages. Available in PDF, EPUB and Kindle. Book excerpt: A guide to contemporary advancements in the field of distal C—H functionalization Remote C—H Bond Functionalizations provides a comprehensive overview on the most recent developments in the field of distal C—H functionalization. The text explores how distal C—H functionalization can be applied in various pharmaceutical and agrochemical industries. With contributions from a noted panel of experts on the topic, the book offers a coherent and comprehensive discussion about different strategies. The contributors cover a broad range of topics including C—H functionalization of palladium/norbornene catalysis, ruthenium-catalyzed remote functionalization, the non-directed distal C(sp2)—H, functionalization, transition metal catalyzed distal para-selective C—H functionalization, and much more. The book also includes information on effective strategies as well as the engineering of templates. Throughout the book, the authors lay the foundations for future research. This important book: Contains the most recent research on one of the most important topics in organic synthesis Provides a broad overview on contemporary advancements in the field of distal C—H functionalization Includes deep insights into distal C—H functionalizations Offers information on applications in various industries Written for organic chemists, chemists working with organometallics, and industrial chemists, Remote C—H Bond Functionalizations presents a systematic compilation of the field.

Download or read book Chemistry Beyond Chlorine written by Pietro Tundo and published by Springer. This book was released on 2016-09-17 with total page 614 pages. Available in PDF, EPUB and Kindle. Book excerpt: Since the industrial revolution, chlorine remains an iconic molecule even though its production by the electrolysis of sodium chloride is extremely energy intensive. The rationale behind this book is to present useful and industrially relevant examples for alternatives to chlorine in synthesis. This multi-authored volume presents numerous contributions from an international spectrum of authors that demonstrate how to facilitate the development of industrially relevant and implementable breakthrough technologies. This volume will interest individuals working in organic synthesis in industry and academia who are working in Green Chemistry and Sustainable Technologies.

Download or read book Advances in Late Metal Carbon Nitrogen Bond Formation for the Synthesis of Substituted Heterocycles written by Nicolas Rotta-Loria and published by . This book was released on 2017 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Late-metal catalyzed cross-couplings have emerged as efficient and selective methodologies for the formation of C-C and C-N bonds. The ability to synthesize complex heterocycles from cheap and abundant starting materials is an invaluable asset to the pharmaceutical industry, given that many pharmaceuticals contain at least one heterocyclic component. This reactivity can be achieved by tuning the steric and electronic properties of ancillary ligands to support metal catalysts in the reaction steps leading to the target substrate. The Stradiotto group has developed several state-of-the-art methodologies involving ligands for palladium catalysis, for both C-C and C-N bond-forming reactions. These methodologies can be amalgamated into a multicomponent reaction platform to synthesize more complex products from simple materials. Chapter 1 outlines this concept with the application of a Mor-DalPhos/Pd catalyst in the one-pot synthesis of indoles from acetone and simple amines involving C-C and C-N bond formation. The robust nature of this method can be extended to include benchtop reaction conditions in a one-step, one-pot synthesis of indoles, thus representing a useful synthetic protocol. While palladium provides a powerful tool for C-C and C-N bond formation, the general trend in catalysis has shifted away from the precious metals toward first row metals as economic alternatives. Nickel complexes have recently emerged as excellent catalysts for a number of amination reactions. The ability to utilize ammonia also represents a sought after reaction, due to the widespread availability and synthetic utility of amino-functionalized products. In this regard, Chapter 2 will focus on the development and application of both commercially available and strategically designed ligand classes for the monoarylation of ammonia with substituted heterocycles. Hydrazine represents an important synthon in synthetic chemistry. It is synthesized on multi-ton scale every year and represents an important building block in many industrial processes. Many synthetic challenges arise from using free hydrazine as reactant, which has led to lethargic growth of its application in the field of late-metal catalyzed C-N bond-formation. However, gold-catalyzed methodologies have been developed utilizing NHC ligands to allow for the hydrohydrazination of alkynes with parent hydrazine. Chapter 4 examines the development and application of a series of (PR3)AuCl complexes for use in such transformations, leading to the identification of the first effective phosphine-bound gold complex for use in the hydrohydrazination of alkynes at room temperature.

Download or read book Cross Coupling Reactions written by Norio Miyaura and published by Springer. This book was released on 2003-07-01 with total page 253 pages. Available in PDF, EPUB and Kindle. Book excerpt: In 1972, a very powerful catalytic cycle for carbon-carbon bond formation was 2 first discovered by the coupling reaction of Grignard reagents at the sp -carbon. Over the past 30 years, the protocol has been substantially improved and expanded to other coupling reactions of Li,B,N,O,Al,Si,P,S,Cu,Mn,Zn,In,Sn, and Hg compounds. These reactions provided an indispensable and simple methodology for preparative organic chemists. Due to the simplicity and rel- bility in the carbon-carbon, carbon-heteroatom, and carbon-metalloid bo- formations,as well as high efficiency of the catalytic process,the reactions have been widely employed by organic chemists in various fields. Application of the protocol ranges from various syntheses of complex natural products to the preparation of biologically relevant molecules including drugs, and of sup- molecules, and to functional materials. The reactions on solid surfaces allow robot synthesis and combinatorial synthesis. Now, many organic chemists do not hesitate to use transition metal complexes for the transformation of org- ic molecules. Indeed, innumerable organic syntheses have been realized by the catalyzed reactions of transition metal complexes that are not achievable by t- ditional synthetic methods. Among these, the metal-catalyzed cross-coupling reactions have undoubtedly contributed greatly to the development of such a new area of “metal-catalyzed organic syntheses”. An excellent monograph for the cross-coupling reactions and other met- catalyzed C-C bond-forming reactions recently appeared in Metal-catalyzed Cross-coupling Reactions (Wiley-VCH,1998).

Download or read book New Strategies in Oxidative Bond Formation written by Karina Targos and published by . This book was released on 2023 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Hydrocarbon feedstocks are plentiful and new methods to engage them in oxidative bond forming reactions are an important frontier of organic synthesis. While photochemistry and electrochemistry offer appealing energy inputs for transforming these feedstocks into value-added products, existing strategies to directly engage unsaturated precursors in bond forming reactions are limited due to the high oxidation potentials required (>2 V vs. SCE). This not only limits functional group tolerance, but also poses nucleophile compatibility challenges. My dissertation work has focused on the development of new activation modes to engage hydrocarbons in oxidative bond forming reactions that overcome the limitations of conventional photoredox and electrosynthetic strategies. The first portion of this thesis is an overview of recent developments in oxidative alkene functionalization (Chapter 1). In particular, the introductory discussion will focus on cationic synthons unlocked by alkene thianthrenation. Recently, our group has developed the electrogeneration of meta-stable dicationic adducts between thianthrene and alkenes under mild anodic oxidation. In my work, we leveraged this alkene activation for allylic bond forming reactions with a range of nucleophiles, such as oxidatively sensitive alkyl amines (Chapter 2). We then outlined a detailed mechanistic study that explains this reactivity and the origin of Z-selectivity (Chapter 3). Unpublished investigations of the scope of Z-selective allylic functionalization will be presented (Chapter 4), as well as insights into diverting the reactivity of alkenylthianthrenium salts from allylic pathways towards difunctionalization reactions (Chapter 5). Additionally, we have leveraged thianthrenium electrophiles for cyclopropane strained-ring synthesis (Chapter 6). Finally, a new electrochemical Z-selective transformation of alkene-thianthrenium adducts will be presented with a focus on outlining the stereodetermining step of this process (Chapter 7). The final chapter will describe another engine to drive oxidative bond formation using visible light energy (Chapter 8). N-phenylphenothiazine-a conventional photoreductant-was coaxed into potent photooxidant behavior in the presence of O2 and lithium cation co-catalyst. This photocatalytic system enables oxidation of benzene for C-N bond formation with nitrogen-containing heterocycles using simple LEDs. Taken together, these two new strategies offer distinct and powerful advantages relative to the state-of-the-art in oxidative construction of new bonds from unsaturated precursors.

Download or read book Science of Synthesis Cross Dehydrogenative Coupling written by Debabrata Maiti and published by Georg Thieme Verlag. This book was released on 2023-09-06 with total page 686 pages. Available in PDF, EPUB and Kindle. Book excerpt: Comprehensive overview of strategies and applications of cross-dehydrogenative coupling methods Cross-Dehydrogenative Coupling (CDC) represents a type of coupling reaction for the construction of a C−C bond or C−heteroatom (C–X) bond directly from C−H and X−H bonds present in the precursors. Since this genre of coupling reaction obviates the need for substrate prefunctionalization, it has an added advantage of high efficiency, atom economy, and environmental friendliness. CDC reactions are triggered by transition-metal catalysts or simply by an oxidants, or by either photocatalysis or electrocatalysis, leading to a hetero- or homo-coupled products with the removal of two hydrogens. Over the years, several CDC strategies have been developed that has made it possible to construct bonds between carbon-hydrogen (C–H) bonds of diverse hybridization. CDC has also streamlined the synthesis and functionalization of various nitrogen, oxygen, and sulfur-containing heterocycles. This volume features a series of chapters systematically covering methods and strategies in CDC, organized primarily on the type of bond being formed. In addition, particular aspects of CDC are highlighted in devoted chapters on topics such as mechanistic aspects, electrochemical and flow methods, transformations in water, natural product synthesis, and enantioselective protocols.

Download or read book C H and C X Bond Functionalization written by Xavi Ribas and published by Royal Society of Chemistry. This book was released on 2013-05-24 with total page 489 pages. Available in PDF, EPUB and Kindle. Book excerpt: Cross-coupling reactions involving C-H and C-X bond functionalisation are commonplace in natural product synthesis and natural products, therapeutic agents, biological probes, and advanced materials. Much attention has been given to understanding the mechanistic strategies used to achieve this, making this a hot topic in recent years. In this edited book, contributions from across the globe examine these strategies, with a particular focus on palladium and copper, as well as iron – an emerging element in this field. Reviewing the recent literature, the book presents an in-depth understanding of the field, guiding the reader to achieving the best synthetic strategies for aromatic functionalisation. Organic and Organometallic chemists, as well as natural product and pharmaceutical scientists, will find this an essential guide to a major transformation currently underway in synthetic chemistry.

Download or read book Methods for C C and C N Bond Formation Using Earth abundant Metals written by Matthew West and published by . This book was released on 2020 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Development of New Transition Metal Catalysts for C N Bond Formation and Continuous Flow Processes for C F Bond Formation written by Nathaniel Hamilton Park and published by . This book was released on 2015 with total page 391 pages. Available in PDF, EPUB and Kindle. Book excerpt: The work presented in this dissertation addresses the development of new methodologies and processes to form carbon-nitrogen (C-N) and carbon-fluorine (C-F) bonds. The development of methods for the formation of C-N and C-F bonds are highly important to chemistry in general and find broad application in many different areas of research. With regard to C-N bond formation, the development of new nickel and palladium catalyst for C-N cross-coupling is presented. Finally, the development of a new process to enable the rapid preparation of aryl fluorides via the Balz-Schiemann reaction is explored. Chapter 1. Development of an Air-Stable Nickel Precatalyst for the Amination of Aryl Chlorides, Sulfamates, Mesylates, and Triflates. A new air-stable nickel precatalyst for C-N cross-coupling is reported. The developed catalyst system displays a greatly improved substrate scope for C-N bond formation to include both a wide range of aryl and heteroaryl electrophiles and aryl, heteroaryl, and alkyl amines. The catalyst system is also compatible with weak base, allowing for the amination of substrates containing base-sensitive functional groups. Chapter 2. Design of New Ligands for the Palladium-Catalyzed Arylation of a- Branched Secondary Amines. In Pd-catalyzed C-N cross-coupling reactions, a-branched secondary amines are difficult coupling partners and often produce low yields of the desired product. To provide a robust method for accessing N-aryl a-branched tertiary amines, new catalysts have been designed to suppress undesired side reactions often encountered when these amine nucleophiles are used. These advances enabled the arylation of a wide array of sterically encumbered amines, highlighting the importance of rational ligand design in facilitating challenging Pd-catalyzed cross-coupling reactions. Chapter 3. Rapid Synthesis of Aryl Fluorides in Continuous Flow via the Balz- Schiemann Reaction. The synthesis of aryl fluorides (ArF) is of critical importance for the development of new and potent pharmaceuticals and agrochemicals. While there have been numerous and intense research efforts focused on developing new fluorination methods, the Balz-Schiemann reaction remains a valuable and efficient means of aryl C-F bond construction from a vast pool of available aryl amines. However, the harsh reaction conditions, modest yields, and often prohibitive safety concerns have limited the general application of this methodology. Here, we have developed a semi-flow process that enables safe handling of the potentially explosive aryl diazonium salt intermediates as well as improved yields of the desired aryl fluoride products. This process has been demonstrated on an array of different aryl and heteroaryl amine substrates containing a variety of different functional groups.

Download or read book Stereoselective Synthesis of Drugs and Natural Products written by Vasyl Andrushko and published by John Wiley & Sons. This book was released on 2013-08-16 with total page 1836 pages. Available in PDF, EPUB and Kindle. Book excerpt: Brings together the best tested and proven stereoselective synthetic methods Both the chemical and pharmaceutical industries are increasingly dependent on stereoselective synthetic methods and strategies for the generation of new chiral drugs and natural products that offer specific 3-D structures. With the publication of Stereoselective Synthesis of Drugs and Natural Products, researchers can turn to this comprehensive two-volume work to guide them through all the core methods for the synthesis of chiral drugs and natural products. Stereoselective Synthesis of Drugs and Natural Products features contributions from an international team of synthetic chemists and pharmaceutical and natural product researchers. These authors have reviewed the tremendous body of literature in the field in order to compile a set of reliable, tested, and proven methods alongside step-by-step guidance. This practical resource not only explores synthetic methodology, but also reaction mechanisms and applications in medicinal chemistry and drug discovery. The publication begins with an introductory chapter covering general principles and methodologies, nomenclature, and strategies of stereoselective synthesis. Next, it is divided into three parts: Part One: General Methods and Strategies Part Two: Stereoselective Synthesis by Bond Formation including C-C bond formation C-H bond formation C-O bond formation C-N bond formation Other C-heteroatom formation and other bond formation Part Three: Methods of Analysis and Chiral Separation References in every chapter serve as a gateway to the literature in the field. With this publication as their guide, chemists involved in the stereoselective synthesis of drugs and natural products now have a single, expertly edited source for all the methods they need.