Download or read book Transition Metal catalyzed Cross coupling of Silicon Electrophiles for the Synthesis of Vinyl and Alkyl Silanes written by Andrew Patrick Cinderella and published by . This book was released on 2018 with total page 533 pages. Available in PDF, EPUB and Kindle. Book excerpt: Vinyl and alkyl silanes are important molecules in organic synthesis, medicinal chemistry, and materials chemistry. The ability of vinyl silanes to participate in Hiyama-Denmark cross-coupling, oxidations, and desilylative halogenations make them highly versatile intermediates. Alkyl silanes engage in similar oxidations and Peterson olefinations. The material properties of alkyl silanes are still under exploration, but they display a profound propensity for freezing point depression when compared to hydrocarbon congeners and amplified lipophilicity of bioactive molecules. I sought to develop methods that could synthesize vinyl and alkyl silanes through transition metal catalysis. Prior to this work, there were limited methods to access vinyl silanes from silyl triflates and secondary alkyl silanes from halosilanes and an organometallic nucleophile. ☐ This dissertation describes the discovery and development of transition metal catalyzed methods to form vinyl and alkyl silanes. We have developed a nickel-catalyzed silyl Heck reaction capable of activating silyl triflates with iodide additives. This methodology allows the first access to silyl triflate electrophiles in cross-coupling, greatly expanding the scope and capabilities of the silyl-Heck reaction. ☐ Advancing the utility of transition metal-catalyzed cross-coupling of halosilanes, I was able to develop a high yielding methodology for the synthesis of secondary alkyl silanes from organozinc halides and iodosilanes; formally a silyl-Negishi reaction. This alkylation strategy was then improved upon by the discovery and development of chlorosilane cross-coupling of Grignard reagents. Exploration of this unprecedented chlorosilane cross-coupling revealed that highly sterically hindered secondary alkyl silanes were capable of being accessed with this methodology. Additionally, mechanistic studies suggest against a typical Kumada cross-coupling mechanism and favor the formation of anionic palladium to perform a substitution at the silicon center.
Download or read book Nickel catalyzed Reductive Coupling of Alkyl Allyl and Vinyl Electrophiles written by Michael R. Prinsell and published by . This book was released on 2013 with total page 187 pages. Available in PDF, EPUB and Kindle. Book excerpt: "The nickel-catalyzed reductive coupling of two organic electrophiles to form new carbon-carbon bonds is a fast emerging field of chemistry, with applications to the synthesis of medicinally interesting compounds. This method is an alternative to traditional transition metal-catalyzed cross-coupling reactions of organic electrophiles with organometallic nucleophiles. This thesis details the author's work towards the development of several reactions to reductively couple organic molecules to form Csp3-Csp3 bonds, including alkyl, allyl and vinyl halides. Chapter 1 delves into the background of traditional metal-catalyzed crosscoupling reactions as well as the advantages and challenges associated with using a reductive method to construct C-C bonds. In particular this chapter presents the specific challenges associated with the formation of a carbon-carbon bond between two Csp3 hybridized carbons. Chapter 2 outlines the development of a mild, general dimerization reaction of alkyl halides. This chapter also focuses on the use of sodium iodide to extend the coupling to molecules that are unreactive to the standard reaction conditions. Chapter 3 details work towards the cross-coupling of two alkyl halides. While cross-selectivity remains a challenge, some potential solutions are discussed. Chapter 4 presents the optimization and reaction scope of the coupling of allyl acetates with secondary alkyl halides, as well as progress towards couplings with primary alkyl halides. In addition, the first report of the catalytic coupling of vinyl bromides with allyl acetates is reported. Chapter 5 focuses on work towards the reductive cyclization of alkyl halides and allyl acetates. Initial results show promising diastereomeric ratios. Chapter 6 details work on the dehydrogenative synthesis of bipyridine and terpyridine ligands. These ligands are useful and are used for many reductive coupling reactions in the Weix group"--Pages vi.
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 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 Base Metal catalyzed Cross couplings of Unconventional Oxygen based Electrophiles and Total Synthesis of Tubingensin A written by Amanda Leanne Silberstein and published by . This book was released on 2014 with total page 494 pages. Available in PDF, EPUB and Kindle. Book excerpt: Transition metal-catalyzed cross-couplings provide a powerful means to assemble carbon-carbon (C-C) and carbon-heteroatom (C-X) bonds. Although halides are the most commonly employed electrophilic partner, phenolic derivatives offer a valuable alternative because phenols are typically inexpensive and readily available. This dissertation describes the development of cross-coupling reactions involving sulfamates and carbamates. Additionally, the total synthesis of tubingensin A utilizing a carbazolyne intermediate is reported. Chapter one reviews the recent advances in transition metal-catalyzed alkylative cross-coupling reactions. This review considers primary and secondary alkylations, tertiary alkylations, and synthetic applications. Particular emphasis is placed on how modern methods have addressed historical challenges. Chapters two and three describe the development of transition metal-catalyzed cross-coupling reactions to form C-C bonds. A nickel-catalyzed Suzuki-Miyaura cross-coupling of aryl sulfamates and carbamates is reported for the formation of sp2-sp2 C-C bonds. An iron-catalyzed Kumada coupling of aryl sulfamates and carbamates is reported for the formation of sp2-sp3 C-C bonds. Chapters four and five pertain to the formation of C-N bonds. The nickel-catalyzed amination of both aryl sulfamates and aryl carbamates are dicussed. The synthetic utility of these methods is highlighted with the synthesis of linezolid, an antibacterial drug, and with sequential, site-selective carbamate and sulfamate cross-couplings. Chapter six describes the total synthesis of natural product tubingensin A. The synthesis features an aryne cyclization to introduce the key vicinal quaternary centers and proceeds efficiently, in only nine linear steps.
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 Development of Nickel Catalyzed Coupling Reactions written by Mikhail Olegovich Konev and published by . This book was released on 2017 with total page 503 pages. Available in PDF, EPUB and Kindle. Book excerpt: Transition metal catalyzed reactions are ubiquitous in the realm of synthetic chemistry, allowing for the strategic construction of complex molecular frameworks of pharmaceuticals, natural products, and synthetic materials. Palladium-catalyzed cross-coupling reactions are part of the foundation of these transformations, insofar as they were recognized with the 2010 Nobel Prize in chemistry. Traditionally, these reactions have relied on aryl and vinyl electrophiles, whereas the alkyl counterparts have only recently begun to emerge in the literature. Nickel has been on the forefront of enantioconvergent alkyl cross--coupling reactions due to its propensity to undergo single electron chemistry. However, under special conditions, it has a unique ability to break strong carbon--oxygen bonds in a stereospecific manner, making research into its reactivity a valuable endeavor to the field of organometallic chemistry.Chapter 1 describes the development of a stereospecific intramolecular alkyl-Heck cyclization of benzylic ethers. The reaction proceeds with inversion at the electrophilic carbon, for the synthesis of methylenecyclopentanes of both extended pi-electron and simple aromatic systems. The enantioenriched products can be effectively derivatized to cyclic alpha-aryl ketones in good yields with good transfer of chirality. Avenues to expand the utility of this reaction have been identified and further studies are ongoing.Chapter 2 discusses the development of nickel-catalyzed cross-electrophile coupling reactions of benzylic esters and aryl halides. An intermolecular reaction proceeds in high yields for primary benzylic esters for the synthesis of pharmacologically relevant diarylmethanes. The corresponding intramolecular cyclization proceeds under mild conditions, demonstrating the first example of a stereospecific cross-electrophile coupling of secondary benzylic esters. A variety of heterocyclic and functionalized substrates are tolerated under the reaction conditions.Chapter 3 examines the development a regio- and stereoselective nickel-catalyzed hydroarylation of alkynes with arylboronic acids. The reaction is facilitated by propargyl carbamates as directing groups. The reaction is tolerant of a range of functional groups and heterocycles. Mechanistic studies reveal that the acidic protons of the arylboronic acid coupling partner serve as the origin of hydrogen. Furthermore, the synthesis of tamoxifen can be completed in two steps from a simple hydroarylation product.
Download or read book Catalysis from A to Z written by Boy Cornils and published by John Wiley & Sons. This book was released on 2020-01-13 with total page 5 pages. Available in PDF, EPUB and Kindle. Book excerpt: Provides a complete and accessible A to Z collection of information on catalysis This updated and enlarged must-have edition of a classic book on catalysis explains the important terms of all aspects of the subject - including biocatalysis, homogeneous catalysis, heterogeneous catalysis - as well as the terms associated with it. It also looks at related topics like spectroscopy or analytical methods. Featuring 20% more content than the previous edition, it comprehensively covers the topic in a clear and concise manner, and includes abbreviations, brief biographic entries of important scientists who have worked in catalysis, trade names, important catalytic processes, named reactions, reactions, and other important keywords in the general field of catalysis. Written by more than 200 top scientists and with more than 15,000 entries on all aspects of catalysis, Catalysis from A to Z: A Concise Encyclopedia, 5th Edition is filled with figures, tables, cross-references, and references. It covers acids, ligands, catalytic reactions in organic synthesis, kinetics and thermodynamics of catalytic reactions, and catalyst labeling. The book also looks at theoretical backgrounds of catalytic reactions, industrial catalytic processes, autoclaves, colloids, nanomaterials, spectroscopically methods for catalyst analysis, and more. Provides all the knowledge scientists need to know about homogeneous, heterogeneous, and biochemical catalysis Includes more than 15,000 keywords in compact entries Newly updated and expanded edition of the bestselling classic Comprehensive, succinct, and easy to use Edited by an experienced team of top editors and authors with contributions from over 200 scientific experts Offers German and French translations of the keywords to help students and non-native English speakers Catalysis from A to Z: A Concise Encyclopedia is an ideal resource for every student, chemist, scientist, and engineer involved in catalytic chemistry, chemical engineering, biochemistry, organic chemistry, and more.
Download or read book Organosilicon Chemistry written by Tamejiro Hiyama and published by John Wiley & Sons. This book was released on 2020-02-18 with total page 566 pages. Available in PDF, EPUB and Kindle. Book excerpt: Provides a unique summary of important catalytic reactions in the presence of silicon A must-have for all synthetic chemists, this book summarizes all of the important developments in the application of organosilicon compounds in organic synthesis and catalysis. Edited by two world leaders in the field, it describes different approaches and covers a broad range of reactions, e.g. catalytic generation of silicon nucleophiles, Si-H Bond activation, C-H bond silylation, silicon-based cross-coupling reactions, and hydrosilylation in the presence of earth-abundant metals. In addition to the topics covered above, Organosilicon Chemistry: Novel Approaches and Reactions features chapters that look at Lewis base activation of silicon Lewis acids, silylenes as ligands in catalysis, and chiral silicon molecules. -The first book about this topic in decades, covering a broad range of reactions -Covers new approaches and novel catalyst systems that have been developed in recent years -Written by well-known, international experts in the areas of organometallic silicon chemistry and organosilicon cross-coupling reactions Organosilicon Chemistry: Novel Approaches and Reactions is an indispensable source of information for synthetic chemists in academia and industry, working in the field of organic synthesis, catalysis, and main-group chemistry.
Download or read book Palladium catalyzed Decarbonylative Cross coupling of Cinnamic Esters with Silicon based Nucleophiles enolates and Oxidative Decarboxylative Cross coupling of Cinnamic Acids with Enolate Precursors written by SangHyun Lee and published by . This book was released on 2018 with total page 78 pages. Available in PDF, EPUB and Kindle. Book excerpt: Transition metal-catalyzed cross-coupling is a powerful methodology to strategically form carbon-carbon or carbon-heteroatom bonds. Advancements in cross-coupling strategies with diverse organometallic nucleophile reagents have been well recognized, however, developments that expand the scope of viable electrophilic partners have only recently been invigorated. Of particular interest is the development of new coupling strategies where both the nucleophilic and electrophilic coupling partner could be derived from oxygenated precursors rather than halogenated precursors, which is the current standard. This thesis describes efforts toward the development of new synthetic methodologies to achieve a-vinylation of enolizable carbonyls in two parts: 1) Pd-catalyzed decarbonylative Hiyama-type cross-coupling of cinnamate esters and aryl silanes and 2) radical-mediated oxidative decarboxylative coupling of cinnamic acids and simple ketones.
Download or read book Transition metal catalyzed Cross coupling of Organic Halides with Enones written by Ruja Shrestha and published by . This book was released on 2012 with total page 344 pages. Available in PDF, EPUB and Kindle. Book excerpt: "Transition-metal-catalyzed formation of carbon-carbon bonds is one of the key synthetic transformations in organic synthesis. Traditional reactions couple an electrophile with a pre-formed organometallic reagent to achieve this transformation. However, organometallic reagents are generally reactive, air and moisture sensitive and suffer from poor functional group compatibility. Advances have been made in the synthesis, use, and handling of organometallic reagents; however, the problem of high reactivity, chemoselectivity, and functional group compatibility remains. Because organometallic reagents are generally synthesized from readily available, bench-stable organic halides, the direct coupling of electrophiles with organic halides in place of an organometallic reagent is desirable. This dissertation details our progress towards this goal for the direct addition of organic halides to carbonyl compounds. Chapter 1 describes the development of conjugate addition reactions from its discovery to the current state-of-the-art. The limitations of the use of organometallic reagents in current methods and the ability to address these limitations with the direct use of organic halides, in the presence of a stoichiometric reducing agent, are discussed. Conjugate additions of organic halides, and tandem conjugate addition-silyl enol ether formation using organometallic reagents have been known for some time. The work presented in this dissertation is the first report on tandem conjugate addition-silyl enol ether formation using organic halides. Chapter 2 describes the coupling of haloalkanes with [alpha], [beta]-unsaturated carbonyl compounds to form silyl enol ethers using a nickel/terpyridine catalyst and stoichiometric manganese reductant. Chapter 3 describes an analogous reaction for the coupling of haloarenes with cyclic alkenones using a nickel/neocuproine catalyst and manganese reductant. The method tolerates a variety of functional groups, including an electrophilic aldehyde and an acidic proton of Naryltrifluoroacetamide (pKa ~ 12). Preliminary mechanistic studies reveal an 'umpolung' mechanism involving the formation of a nickel-silyloxyallyl species, which undergoes reduction prior to the reaction with an organic halide to form the desired silyl enol ether. Unlike traditional cross-coupling methods, the reactions described in Chapters 2 and 3 can be assembled on the benchtop without special precautions to exclude air. The reactions proceed under mild reaction conditions to provide good yields of silyl enol ethers. The methods demonstrate that the direct coupling of organic halides with electrophiles in the presence of a stoichiometric reductant can minimize the number of steps required for a desired transformation, increase the ease of manipulation, and improve functional group compatibility. Chapter 4 outlines a research project focused on the addition of organic halides to aldehydes and imines using a palladium catalyst. While Chapters 2 and 3 describe the use of metallic reducing agents, Chapter 4 addresses the possibility of using sulfur(IV) reagents as terminal reductants. The desired catalytic transformation is proposed to involve a novel S-O bond reductive elimination step. Stoichiometric studies to observe the desired reductive elimination from palladium and the discovery of copper-mediated radical reaction for tosylation of phenols during the course of the study are discussed"--Page vii-viii.
Download or read book Development of Nickel catalyzed Stereospecific Cross coupling Reactions written by Buck L. H. Taylor and published by . This book was released on 2012 with total page 171 pages. Available in PDF, EPUB and Kindle. Book excerpt: Transition-metal catalyzed cross-coupling reactions are powerful methods for the synthesis of natural products and medicinal compounds. Cross-coupling reactions of secondary alkyl electrophiles are currently more challenging than those of aryl or vinyl halides, but these reactions enable the construction of tertiary stereogenic centers with control of configuration. Several methods have been reported for the stereoconvergent cross-coupling of alkyl halides using chiral nickel catalysts. Herein, we report the development of a stereospecific cross-coupling reaction of enantioenriched benzylic ethers using achiral nickel catalysts. We initially performed mechanistic studies to determine the stereochemical course of established nickel-catalyzed cross-coupling reactions. A deuterium-labeled alkylborane reagent was used to establish that transmetalation from boron to nickel occurs with retention of configuration. In addition, these studies establish that alkylnickel intermediates are stereochemically stable under these cross-coupling conditions. A stereospecific cross-coupling reaction of benzylic ethers with alkyl Grignard reagents has been developed. Enantioenriched benzylic ethers, derivatives of easily synthesized chiral secondary alcohols, undergo cross-coupling with high enantiospecificity using an achiral nickel catalyst. The method was applied to the asymmetric synthesis of a biologically active diarylethane, a common structural motif in medicinally relevant compounds. Initial mechanistic studies are consistent with a rate-limiting oxidative addition that is facilitated by a magnesium Lewis-acid. The cross-coupling method has been extended to include aryl Grignard reagents for the asymmetric synthesis of triarylmethanes. The reaction proceeds in high enantiospecificity and employs an ether leaving group capable of chelating to magnesium ions. The method was applied to the asymmetric synthesis of an anti-breast-cancer agent.
Download or read book Nickel catalyzed Electrophile Cross coupling of Aryl Halides with Alkyl Halides written by Daniel A. Everson and published by . This book was released on 2013 with total page 264 pages. Available in PDF, EPUB and Kindle. Book excerpt: "This thesis details the author's contributions to the emerging field of electrophile cross-couplings. This new field is related to the well-established field of conventional cross-coupling that uses transition metal-catalysts to facilitate coupling reactions between electrophile-nucleophile pairs. Electrophile cross-coupling uses a conceptually different approach because it seeks to selectively join two different electrophiles with a transition metal-catalyst. The issue of developing cross-selective reactions is the central challenge addressed. Chapter 1 details recent advances and the state-of-the-art in conventional cross-coupling only for the purpose of conceptual comparison to electrophile cross-coupling. Additionally, a review of similar coupling reactions and their mechanisms are presented with the earliest examples of the unique reactivity that guided development of the reactions in this thesis. Chapter 2 details the first cross-selective nickel-catalyzed electrophile cross-coupling of iodoarenes with iodoalkanes. The new method displays exceptional functional group compatibility (-C(O)Me, -NHBoc, 1° and 2° alkyls, -OH) and the catalyst shows chemoselective reaction at C-I bonds over C-B bonds on bifunctional substrates. Mechanistic studies reveal that the reaction likely proceeds without the intermediacy of a carbon nucleophile, and that dimeric by-products arise from disproportionation of nickel intermediates. Chapter 2 also summarizes a detailed mechanistic study conducted in our lab that indicates the cross-coupled product is formed by a radical chain mechanism. Chapter 3 expands on the results of Chapter 2 by increasing the scope of the method to include bromo- and chloroarenes for the first time. Additional competition experiments reveal that the new catalysts and reaction conditions are chemoselective for the cross-coupling of two electrophilic C-Br bonds over conventional cross coupling of C-Br bonds with C-B, C-Sn, or C-Si bonds. Further mechanistic work reveals that [upsilon] [is proportional to] [bromoalkane][^x][catalyst][^y]/[bromoarene][^z] (x, y, and z are positive numbers and could be non-integers). Chapter 4 presents the first electrophile cross-couplings of halogenated pyridines with alkyl bromides. Scope and limitations are discussed in the context of improving the method. Chapter 5 details the effect of additives on other related electrophile coupling reactions"--Pages vii-viii.
Download or read book Nickel catalyzed Reductive Coupling of Aryl Halides with Alkyl Electrophiles written by Lukiana L. Anka-Lufford and published by . This book was released on 2015 with total page 208 pages. Available in PDF, EPUB and Kindle. Book excerpt: "The direct transition-metal catalyzed cross-coupling of two different electrophiles is a fast emerging synthetic method, as it avoids the use of carbon nucleophiles. Despite being a synthetically valuable strategy, a central challenge of cross-electrophile coupling is achieving selectivity for cross-coupled product over dimerization products. This thesis details the author's work towards the development of cross-selective methods for the formation of Csp2-Csp3 bonds. Chapter 1 introduces the conventional cross-coupling method of forming C-C bonds and highlights the advantages of using the reductive cross-electrophile coupling approach instead. The selectivity challenges associated with reductive cross-coupling and the origins of selectivity in the cross-coupling reactions of aryl halides with allylic acetates and benzyl mesylates are discussed. Motivations towards the adaptation of our cross-electrophile coupling methods to more environmentally responsible solvents and reductants are also described. Chapter 2 details a general protocol for the coupling of aryl halides with allylic acetates and shows that high cross-selectivity can be achieved with the use of a terpyridine nickel catalyst. Strength's of the method are presented such tolerance for electrophilic (ketone (71%), aldehyde (70%)) and acidic (sulfonamide (73%), trifluoroacetamide (64%)) substrates and the ability to couple with a variety of substituted allylic acetates. The reductive method addresses the regioselectivity and substrate availability limitations observed in past approaches to allylated arenes. Chapter 3 presents the first synthesis of diarylmethanes from benzyl mesylates and aryl halides using cobalt phthalocyanine (Co(Pc)), a new co-catalyst for radical generation that is compatible with nickel-catalysis. Studies are shown demonstrating the orthogonal reactivity of (dtbbpy)Ni and Co(Pc) and the application of this selectivity to the coupling of functionalized benzyl mesylates with aryl halides. The adaptation of the method to the less reactive benzyl phosphate ester and an enantioconvergent reaction are also presented. Chapter 4 shows studies towards the adaptation of cross-electrophile coupling to more environmentally friendly solvents and reductants. Here, a homogeneous, two electronic organic reductant, 1,2,2-tetrakis(dimethylamino)ethylene (TDAE), is shown to be effective for nickel-catalyzed cross-electrophile coupling in various green solvents such as propylene carbonate and acetonitrile. These reactions are close in yield to our best-reported results in amide or urea solvents using zinc or manganese as the reductant. Chapter 5 describes initial studies towards nickel-catalyzed decarbonylative coupling reactions of acid chloride derivatives with aryl and alkyl halides and nickel-catalyzed coupling reactions of aryl halides with small cyclic alkyl bromides and oxetane tosylate. Further optimization strategies are presented."--Pages viii-ix.
Download or read book Advancements in Nickel catalyzed Cross electrophile Coupling written by Keywan Alexander Johnson and published by . This book was released on 2019 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: In this thesis, the extension of cross-electrophile coupling to engage vinyl halides, organic chlorides, and dihalides for cyclization will be described in detail. Chapter 1 will provide an introduction to cross-electrophile coupling and the current state of the art for these transformations. Chapter 2 describes the development of improved coupling conditions for the nickel-catalyzed cross-electrophile coupling of vinyl halides with alkyl halides. The application of these conditions to aryl-alkyl coupling, substrate scope and limitations, and preliminary mechanistic insights are also discussed. Chapter 3 describes studies performed for the coupling of aryl and alkyl chlorides. The effects of a dual ligand system on reaction selectivity, as well as implications of dimethoxyethane and diglyme nickel precatalysts are also conferred. Chapter 4 provides a survey of macrocyclization methodologies and details the application of cross-electrophile coupling to the synthesis of macrocyclic rings. Efforts towards the total synthesis of (+/- )-Recifeiolide are also discussed.
Download or read book Metal Vinylidenes and Allenylidenes in Catalysis written by Christian Bruneau and published by John Wiley & Sons. This book was released on 2008-06-23 with total page 360 pages. Available in PDF, EPUB and Kindle. Book excerpt: Focusing on preparation and applications in synthesis and catalysis, this book finally closes a gap in the literature by summarizing this hot topic for the first time. As such, it gathers in one volume the key features of metal vinylidene and allenylidene complexes as well as reactive species and covers applications in metathesis, polymerization, molecular materials, carbon rich compounds and fine chemical production. The emphasis here is on the selective transformations of alkynes and enynes plus simple and complex molecules containing a triple C-C bond. The result is a must-have ready reference for organic, catalytic, complex, theoretical and polymer chemists, as well as those working with/on organometallics.
Download or read book Transition Metal Catalyzed Enantioselective Allylic Substitution in Organic Synthesis written by Uli Kazmaier and published by Springer Science & Business Media. This book was released on 2011-10-29 with total page 354 pages. Available in PDF, EPUB and Kindle. Book excerpt: Giovanni Poli, Guillaume Prestat, Frédéric Liron, Claire Kammerer-Pentier: Selectivity in Palladium Catalyzed Allylic Substitution.- Jonatan Kleimark and Per-Ola Norrby: Computational Insights into Palladium-mediated Allylic Substitution Reactions.- Ludovic Milhau, Patrick J. Guiry: Palladium-catalyzed enantioselective allylic substitution.- Wen-Bo Liu, Ji-Bao Xia, Shu-Li You: Iridium-Catalyzed Asymmetric Allylic Substitutions.- Christina Moberg: Molybdenum- and Tungsten-Catalyzed Enantioselective Allylic Substitutions.- Jean-Baptiste Langlois, Alexandre Alexakis: Copper-catalyzed enantioselective allylic substitution.- Jeanne-Marie Begouin, Johannes E. M. N. Klein, Daniel Weickmann, B. Plietker: Allylic Substitutions Catalyzed by Miscellaneous Metals.- Barry M. Trost, Matthew L. Crawley: Enantioselective Allylic Substitutions in Natural Product Synthesis.
