Carbon-nitrogen Bond Formation Via Tandem Carbon-hydrogen (C-H) and Nitrogen-hydrogen (N-H) Bond Functionalization

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Total Pages : 342 pages
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Book Synopsis Carbon-nitrogen Bond Formation Via Tandem Carbon-hydrogen (C-H) and Nitrogen-hydrogen (N-H) Bond Functionalization by : Abhishek A. Kantak

Download or read book Carbon-nitrogen Bond Formation Via Tandem Carbon-hydrogen (C-H) and Nitrogen-hydrogen (N-H) Bond Functionalization written by Abhishek A. Kantak and published by . This book was released on 2014 with total page 342 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Catalytic Methods for Carbon-carbon and Carbon-nitrogen Bond Formation

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ISBN 13 :
Total Pages : 511 pages
Book Rating : 4.:/5 (911 download)

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Book Synopsis Catalytic Methods for Carbon-carbon and Carbon-nitrogen Bond Formation by : Stephen David Ramgren

Download or read book Catalytic Methods for Carbon-carbon and Carbon-nitrogen Bond Formation written by Stephen David Ramgren and published by . This book was released on 2014 with total page 511 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation describes the study of metal-catalyzed cross-coupling reactions to construct carbon-carbon and carbon-heteroatom bonds. The key feature of much of this work is the use of inexpensive Ni and Fe catalysts to enable the coupling of unconventional electrophilic substrates, specifically aryl O-sulfamates and O-carbamates. The ability to use O-sulfamates and O-carbamates in catalytic processes is notable, as these substrates are readily derived from phenols and can be used for directed arene functionalization. Chapter one provides a summary of the efforts towards using alcohol-based solvents for the Suzuki-Miyaura cross-coupling reaction. Emphasis is placed on the cross-coupling of heterocycles, which are commonly encountered in natural product synthesis and in the pharmaceutical sector. Chapters two, three, and four describe carbon-nitrogen bond forming reactions. Chapter two pertains to the nickel-catalyzed amination of sulfamates, which culminated in the synthesis of the antibacterial drug, linezolid. Chapter three covers the amination of aryl O-carbamates and their use in sequential functionalization/site-selective cross-couplings. Chapter four describes a more user-friendly variant of the amination reaction, which relies on a bench-stable Ni(II) precatalyst, rather than a more commonly used Ni(0) precatalyst. Chapters five, six, and seven focus on carbon-carbon bond formation via Fe-, Ni- and Pd-mediated processes. Chapter five pertains to iron-catalyzed couplings of sulfamates and carbamates to generate sp2-sp3 carbon-carbon bonds. This method can be used to assemble sterically-congested frameworks. Chapter six describes the nickel-catalyzed Suzuki-Miyaura reactions of halides and phenol derivatives in `green' solvents, which was applied to the preparative scale assembly of bis(heterocycles) using low nickel catalyst loadings. Chapter seven pertains to the acetylation of arenes using palladium catalysis, which provides a simple and efficient means for the construction of a variety of aryl methyl ketones.

New Approaches to Carbon-nitrogen Bond Formation

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Total Pages : 162 pages
Book Rating : 4.:/5 (776 download)

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Book Synopsis New Approaches to Carbon-nitrogen Bond Formation by : Sarah Hindennach

Download or read book New Approaches to Carbon-nitrogen Bond Formation written by Sarah Hindennach and published by . This book was released on 2011 with total page 162 pages. Available in PDF, EPUB and Kindle. Book excerpt:

The Chemistry of Carbon Nitrogen Double Bonds

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ISBN 13 :
Total Pages : 818 pages
Book Rating : 4.X/5 (1 download)

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Book Synopsis The Chemistry of Carbon Nitrogen Double Bonds by : Saul Patai

Download or read book The Chemistry of Carbon Nitrogen Double Bonds written by Saul Patai and published by . This book was released on 1970-01-15 with total page 818 pages. Available in PDF, EPUB and Kindle. Book excerpt: The most complete resource in functional group chemistry Patai's Chemistry of Functional Groups is one of chemistry's landmark book series in organic chemistry. An indispensible resource for the organic chemist, this is the most comprehensive reference available in functional group chemistry. Founded in 1964 by the late Professor Saul Patai, the aim of Patai's Chemistry of Functional Groups is to cover all the aspects of the chemistry of an important functional group in each volume, with the emphasis not only on the functional group but on the whole molecule.

Carbon-nitrogen Bond Formation Via Catalytic Alcohol Activation

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ISBN 13 : 9789403400471
Total Pages : 147 pages
Book Rating : 4.4/5 (4 download)

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Book Synopsis Carbon-nitrogen Bond Formation Via Catalytic Alcohol Activation by : Tao Tan

Download or read book Carbon-nitrogen Bond Formation Via Catalytic Alcohol Activation written by Tao Tan and published by . This book was released on 2017 with total page 147 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Remote C-H Bond Functionalizations

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Publisher : John Wiley & Sons
ISBN 13 : 3527346678
Total Pages : 450 pages
Book Rating : 4.5/5 (273 download)

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Book Synopsis Remote C-H Bond Functionalizations by : Debabrata Maiti

Download or read book Remote C-H Bond Functionalizations written by Debabrata Maiti and published by John Wiley & Sons. This book was released on 2021-04-26 with total page 450 pages. Available in PDF, EPUB and Kindle. Book excerpt: A guide to contemporary advancements in the field of distal C-H functionalizations An important and dynamic topic within the modern field of organic synthesis, selective functionalization of C-H bonds can be used in a variety of applications across the pharmaceutical and agrochemical industries. Remote C-H Bond Functionalizations presents an inclusive account of the most recent developments and potential applications of performing variegated functionalizations selectively at the distal positions of organic compounds. Featuring contributions by an international team of experts, this authoritative volume provides deep insight into distal functionalizations, including detailed discussion of mechanisms, the engineering of templates, and the design of strategies. The text covers a diverse 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. Reviewing contemporary advancements in the field while laying the foundation for future research, this important resource: Provides the most recent research and thorough coverage of the subject available in a single volume Offers practical information on C-H functionalizations in various industries Includes an up-to-date introduction to distal C-H functionalizations Remote C-H Bond Functionalizations is a must-read for every synthetic chemist, including chemists working with organometallics, organic chemists and researchers, and industrial chemists.

Sp2 Carbon-Hydrogen Bond (C-H) Functionalization

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Total Pages : 226 pages
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Book Synopsis Sp2 Carbon-Hydrogen Bond (C-H) Functionalization by : Sirilata Yotphan

Download or read book Sp2 Carbon-Hydrogen Bond (C-H) Functionalization written by Sirilata Yotphan and published by . This book was released on 2010 with total page 226 pages. Available in PDF, EPUB and Kindle. Book excerpt: Abstract sp2 Carbon-Hydrogen Bond (C-H) Functionalization by Sirilata Yotphan Doctor of Philosophy in Chemistry University of California, Berkeley Professor Robert G. Bergman, Chair Chapter 1. A review of the Bergman/Ellman group literature on rhodium-catalyzed direct sp2 C-H bond functionalization reactions is presented. In addition, some well-known late transition-metal catalyzed sp2 C-H bond functionalization reactions are described. These synthetic methods have valuable applications for organic chemistry and enable access to a number of interesting organic compounds and derivatives. These examples highlight the importance of this type of transformation and provide the background from which the results described in Chapters 2-5 may be viewed. Chapter 2. Bridgehead bicyclic unsaturated enamines were prepared by a tandem rhodium-catalyzed C-H bond activation/alkenylation/electrocyclization of alkyne-tethered unsaturated imines. These strained bicyclic enamines exhibit unique reactivity: for example, they lead to N-alkylated products upon treatment with alkylating reagents and undergo double bond isomerization to alleviate ring strain upon reduction. Chapter 3. An efficient method is reported for the preparation of multicyclic pyridines and quinolines by a rhodium-catalyzed intramolecular C-H bond functionalization process. The method shows good scope for branched and unbranched alkyl substituents on the pyridine ring and at the R position of the tethered alkene group. Starting materials capable of undergoing olefin isomerization to provide terminal 1,1-disubstituted alkenes also proved to be effective substrates. Chapter 4. A method for the direct arylation of benzotriazepines is reported, employing an aryl iodide as the coupling partner, copper iodide as the catalyst, and lithium tert-butoxide as the base. A variety of electron-rich, electron-poor, and sterically hindered aryl iodides are compatible with the reaction conditions. The arylation reaction can also be performed outside a glovebox in air without a significant decrease in yield. Furthermore, convenient microwave conditions for carrying out this transformation are reported. Chapter 5. The reaction of isopropyl Grignard reagent and 3-bromoquinoline leads to formation of interesting 3,4-disubstituted quinoline products in significant yields. This transformation was extensively studied for 3-bromoquinoline as the substrate, isopropyl magnesium chloride as the nucleophile, and a Brønsted acid or 3-bromopropene as electrophiles. A brief survey of this transformation, identification of the reaction limitations, and a suggested mechanism are reported in this Chapter.

Developing New Routes Towards C-N Bond Formation Via Electron Upconversion

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Total Pages : 0 pages
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Book Synopsis Developing New Routes Towards C-N Bond Formation Via Electron Upconversion by : Quintin Dale Elliott (Jr.)

Download or read book Developing New Routes Towards C-N Bond Formation Via Electron Upconversion written by Quintin Dale Elliott (Jr.) and published by . This book was released on 2022 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: The work disclosed in this dissertation explores using two-center/three-electrons and electron upconversion in C-N bond formation. In particular, three areas will be discussed in detail: 1) computation exploration into intermolecular C-N bond formation between a methyl radical and various nitrogen nucleophiles; 2) DFT calculations are used to investigate electron upconversion in an intramolecular C-N bond formation between dimethyl malonitrile and anilines; 3) An intramolecular C(sp3)-H amidation which opens a new path to hydroxyisoindolines. Chapter One begins with a broad overview of N-heterocycles, their applications, and general approaches for constructing them. One approach, C-H activation, is expanded upon as a promising method for constructing and functionalizing N-heterocycles. Four general methods for C-H activation are introduced: 1) direct activation, 2) C-H activation with delayed C-N bond formation, 3) nitrogen assisted C-H activation, and 4) independent N-H/C-H activation. This final approach activates both the N-H and C-H bonds and transforms them into reactive intermediates. For instance, the formation of a radical and a (persistent) anion (typically C-radical and N-anion) can be used to productively form a three-electron bond. Due to the extra electron is "upconverted" and creates a species with a higher oxidation potential capable of being oxidized by a mild oxidant, such as molecular oxygen. Chapter Two further expands upon the concept of "electron upconversion" as a synthetic method for constructing C-N bonds. When the orbitals of the two centers mix two new orbitals are created, a bonding and anti-bonding orbital. When three electrons are used to make a bond two of those electrons will be stabilized in the bonding orbital and a single electron will be destabilized in an anti-bonding orbital. The result is a net stabilization of a single electron. Additionally, by moving a single electron from a non-bonding orbital to a higher energy anti-bonding orbital one transforms the reactant from a weaker reductant to a more potent reductant, allowing for a facile electron transfer. Chapter Three uses DFT calculations to probe the effects solvent polarity has on intermolecular three-electron bond formations as well as the ability to trap a methyl radical with a range of N-nucleophiles. Chapter Four explores if oxidation under basic conditions allows the formation of three-electron bonds (resulting in "upconverted" highly-reducing radical-anions). The benefit of this "upconversion" process is in the ability to use milder oxidants (e.g., O2) and to avoid high-energy intermediates. Comparison of the two- and three-electron pathways using quantum mechanical calculations reveals that not only does the absence of a strong oxidant shut down two-electron pathways in favor of a three-electron path but, paradoxically, weaker oxidants react faster with the upconverted reductants by avoiding the inverted Marcus region for electron transfer. Chapter Five presents An intramolecular C(sp3)-H amidation proceeds in the presence of t-BuOK, molecular oxygen, and DMF. This transformation is initiated by the deprotonation of an acidic N-H bond and selective radical activation of a benzylic C-H bond towards hydrogen atom transfer (HAT). Cyclization of this radical-anion intermediate en route to a two-centered/three-electron (2c,3e) C-N bond removes electron density from nitrogen. As this electronegative element resists such an "oxidation", making nitrogen more electron rich is key to overcoming this problem. Remarkably, this reaction also converts a weak reductant into much a stronger reductant. Such "reductant upconversion" allows mild oxidants like molecular oxygen to complete the first part of the cascade. In contrast, the second stage of NH/CH activation forms a highly stabilized radical-anion intermediate incapable of undergoing electron transfer to oxygen. Because the oxidation is unfavored, an alternative reaction path opens via coupling between the radical anion intermediate and either superoxide or hydroperoxide radical. The hydroperoxide intermediate transforms into the final hydroxyisoindoline products under basic conditions.

Reversible Carbon-nitrogen Bond Formation Between Organocobaltnitrosyls and Alkenes

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ISBN 13 :
Total Pages : 222 pages
Book Rating : 4.:/5 (824 download)

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Book Synopsis Reversible Carbon-nitrogen Bond Formation Between Organocobaltnitrosyls and Alkenes by : Paul Norbert Becker

Download or read book Reversible Carbon-nitrogen Bond Formation Between Organocobaltnitrosyls and Alkenes written by Paul Norbert Becker and published by . This book was released on 1982 with total page 222 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Biocatalytic Methods for Carbon-nitrogen Bond Formation Via Hemoprotein-catalyzed Group Transfer Reactions

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ISBN 13 :
Total Pages : 254 pages
Book Rating : 4.:/5 (129 download)

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Book Synopsis Biocatalytic Methods for Carbon-nitrogen Bond Formation Via Hemoprotein-catalyzed Group Transfer Reactions by : Viktoria Steck

Download or read book Biocatalytic Methods for Carbon-nitrogen Bond Formation Via Hemoprotein-catalyzed Group Transfer Reactions written by Viktoria Steck and published by . This book was released on 2019 with total page 254 pages. Available in PDF, EPUB and Kindle. Book excerpt: "Our group has recently established that heme-containing proteins, in particular myoglobin and cytochrome P450s, constitute promising biocatalysts for the formation of carbon-nitrogen and carbon-carbon bonds via nitrene and carbene transfer reactions, a class of synthetically valuable transformations not occurring in nature. Building upon this work, a first goal of this research was to improve the scope and efficiency of these nitrene transfer biocatalysts for C-H amination reactions. To this end, we identified a novel, unusual P450-type enzyme named XplA, which catalyzes the intramolecular C-H amination of arylsulfonyl azide substrates with a significant enhancement of activity and chemoselectivity in comparison to other P450s, which efficiency in this reaction is limited by the generation of reduced byproducts. Primary kinetic isotope effect studies revealed that the mechanism proceeds with C-H bond activation as the rate limiting step and provided insights into the competition between productive vs. non-productive nitrene transfer pathways. Furthermore, we discovered that non-heme Rieske dioxygenases are viable C- H amination biocatalysts and explored their potential value in nitrene transfer reactions by means of protein engineering, large scale reactions in a bioreactor, and analysis of their reaction and substrate scope. In a second part, we expanded and modulated the reactivity of myoglobin biocatalysts in carbene transfer reactions. A series of artificial myoglobin-based metalloenzymes containing manganese, iron, cobalt, ruthenium, rhodium and iridium were investigated for cyclopropanation and Y-H (Y = N, S) carbene insertion reactions. Engineered variants containing a ruthenium cofactor were found to be excellent S-Hinsertion catalysts, while variants harboring an iridium cofactor were capable of C-H insertion reactions not supported by the parent protein. Next, we demonstrated how cofactor variation in combination with mutations of the proximal ligand anchoring the metalloporphyrin in the active site pocket drastically influences catalyst chemoselectivity. Specifically, we developed a serine-ligated cobalt-porphyrin variant that favors the more challenging olefin cyclopropanation reaction in the presence of competing functional groups. In contrast, the native protein with a histidine-ligated heme cofactor selectively undergoes the complementary Y-H (Y = N, Si) insertion reaction in the presence of unsaturated bonds. In a further study, we successfully extended the substrate scope of engineered myoglobin 'carbene transferases' for realizing N-H insertion reactions between benzyl- and alkylamines and different diazo precursors, which was previously not reported for other hemoproteins, thereby enabling access to valuable functionalized benzyland alkylamines. Finally, we devised a biocatalytic strategy for the asymmetric synthesis of chiral amines via myoglobin-catalyzed N-H insertion. Achieving high enantioselectivity in carbene-mediated N-H insertion reactions has been notoriously challenging. To this end, reactions involving a combination of evolved myoglobin variants with engineered diazo compounds led to the first report and highest enantioselectivity achieved by a biocatalyst in this reaction to date. In addition, stereodivergent biocatalysts were developed to obtain both mirror-image forms of chiral anilines. Altogether, these studies highlight how protein engineering provides a powerful strategy for expanding the biocatalytic toolbox toward synthetically useful yet challenging abiological biotransformations under environmentally friendly and sustainable conditions"--Pages xi-xii.

Advances in Late-Metal Carbon-Nitrogen Bond Formation for the Synthesis of Substituted Heterocycles

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Total Pages : 0 pages
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Book Synopsis Advances in Late-Metal Carbon-Nitrogen Bond Formation for the Synthesis of Substituted Heterocycles by : Nicolas Rotta-Loria

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.

Activation of Carbon-Hydrogen Bonds Mediated by Ru(II) Complexes

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Book Synopsis Activation of Carbon-Hydrogen Bonds Mediated by Ru(II) Complexes by :

Download or read book Activation of Carbon-Hydrogen Bonds Mediated by Ru(II) Complexes written by and published by . This book was released on 2004 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: The RuII complex TpRu(CO)(NCMe)Me (Tp = hydridotris(pyrazolyl)borate) initiates carbon-hydrogen bond activation at the 2-position of furan and thiophene to produce methane and TpRu(CO)(NCMe)Ar (Ar = 2-furyl or 2-thienyl). Solid-state structures have been determined for TpRu(CO)(NCMe)(2-thienyl) and [TpRu(CO)(m-C, S-thienyl)]2. The complex TpRu(CO)(NCMe)(2-furyl) serves as a catalyst for the formation of 2-ethylfuran from ethylene and furan. Similar catalytic reactivity was observed with TpRu(CO)(NCMe)(2-thienyl) for the production of 2-ethylthiophene. Density functional theory (DFT) calculations of the C-H activation of furan by {(TAB)Ru(CO)Me} (TAB = tris(azo)borate) indicate that the C-H activation sequence does not proceed through a RuIV oxidative addition intermediate. The reaction of TpRu(CO)(NCMe)Me and pyrrole forms TpRu(CO){k 2-N, N-(H)N=C(Me)(NC4H3)}. The formation of complex TpRu(CO){k2-N, N-(H)N=C(Me)(NC4H3)} involves the cleavage of the N-H bond and 2-position C-H bond of pyrrole as well as a C-C bond forming step between pyrrole and the acetonitrile ligand of {TpRu(CO)(NCMe)}. Mechanistic studies indicate that the most likely reaction pathway involves initial metal-mediated N-H activation of pyrrole to produce TpRu(CO)(NCMe)(N-pyrrolyl) followed by C-C bond formation and proton transfer. Complex TpRu(CO)(NCMe)(N-pyrrolyl) has been independently prepared. At elevated temperatures, TpRu(CO)(NCMe)(N-pyrrolyl) converts to TpRu(CO){k2-N, N-(H)N=C(Me)(NC4H3)}. Single crystal X-ray analysis has been achieved for TpRu(CO)(NCMe)(N-pyrrolyl), [TpRu(CO)(NCMe)(h1-O-OC4H8) and TpRu(CO){k2-N, N-(H)N=C(Me)(NC4H3)}. Computational studies support the suggested selectivity for initial N-H bond cleavage in preference to C-H bond activation. Rational design for a more electron-poor hydroarylation catalyst was discussed. Synthesis of Mp (Mp = tris(pyrazolyl)methane) complexes of the type [MpRu(PPh3)(CO)H]BAr'4, [MpRu(PPh3)(CO)Cl]BAr'4].

Transition Metal-catalyzed Functionalization of Carbon-hydrogen Bonds in Alkenes

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Book Synopsis Transition Metal-catalyzed Functionalization of Carbon-hydrogen Bonds in Alkenes by : Xiaolin Qian

Download or read book Transition Metal-catalyzed Functionalization of Carbon-hydrogen Bonds in Alkenes written by Xiaolin Qian and published by . This book was released on 2023 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Alkenes can undergo a variety of chemical reactions to form more complex molecules with a range of functional groups. This makes them useful starting materials for synthesizing a wide range of organic compounds. Chapter I provided an overview of the development history of alkenyl C8́2H bond activation. The early reactions of C8́2H compounds with metal complexes, as well as stoichiometric activation of the transition metal-activated C-H bond, were discussed. Then the first successful and efficient organometallic-catalyzed transformations of a C8́2H bond, the first transition metal-catalyzed vinylic C-H functionalization, and the first transition metal-catalyzed olefinic C-H functionalization under mild conditions were demonstrated. Finally, enantioselective vinylic C-H functionalization was discussed. In Chapter II, a method for enantioselective vinylic C(sp2)8́2H bond activation using a Ru(II) catalyst and a chiral transient directing group was developed. Chiral amine was also utilized to control the Z/E stereoselectivity. The method demonstrated a broad substrate scope with good yield, high Z/E ratio stereoselectivity, and excellent enantioselectivity. Its synthetic utility was demonstrated by the synthesis of key structural motifs of particularly useful natural products and pharmaceutical compounds. Additionally, a rare vinylic C8́2H bond activated ruthenic complex was isolated and determined by single-crystal X-ray diffraction. The methodology suggested in this work is expected to facilitate the further development of asymmetric vinylic C8́2H functionalization reactions. In Chapter III, a practical and efficient methodology for Ru(II)-catalyzed enantioselective alkenyl C-H bond functionalization of indole-substituted acrylaldehyde derivatives via the chiral transient directing group (CTDG) strategy to obtain optically active pyrrolo[1,2-a]indole derivatives was suggested. The methodology resulted in a series of optically active products with good yields (up to 80%), good stereoselectivity (up to 25.0:1 Z/E), and excellent enantioselectivity (up to 95% ee). Furthermore, synthetic transformations were explored. Chapter IV presented the first demonstration of a sequentially composed catalytic substitution reaction of alkenes for building multi-amido methylated derivatives while reserving the Ï0- components. The process involved a simple Fe (III)-catalyst and bisamidomethane reagent, which directly and selectively transformed Îł-substituted styrenes into several biologically and pharmaceutically relevant N-heterocycles through tandem processes.

Enantioselective Iridium-catalyzed Carbon–carbon and Carbon–nitrogen Bond Formations

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Total Pages : 1462 pages
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Book Synopsis Enantioselective Iridium-catalyzed Carbon–carbon and Carbon–nitrogen Bond Formations by : Leyah Ashley Schwartz

Download or read book Enantioselective Iridium-catalyzed Carbon–carbon and Carbon–nitrogen Bond Formations written by Leyah Ashley Schwartz and published by . This book was released on 2020 with total page 1462 pages. Available in PDF, EPUB and Kindle. Book excerpt: Formation of new C–C bonds is a mainstay of modern molecule construction, however methods for the asymmetric construction of these scaffolds has been limited by the use of premetalated reagents or the use of catalytic methods that still require the use of stoichiometric metallic reductants. The Krische group’s approach to this bond formation utilizes the concepts of transfer hydrogen and carbonyl addition to form C–C bonds. These processes proceed through the in situ formation of a transient allylmetal species which then undergoes carbonyl addition. The research presented herein describes the development of several methods for the enantioselective construction of new C–C bonds, utilizing allenes to form nucleophilic allylmetal complexes that react with carbonyl electrophiles. Additionally, a method for the enantioselective construction of new C–N bonds is described, utilizing branched allylic acetates to form allylmetal complexes that react in an electrophilic manner with non-redox active primary and secondary amine nucleophiles

Carbon-nitrogen Bond Formations Via the Stille Cross-coupling Reaction and Investigations of the Cross-coupling of Terminal Dibromoolefins with Organostannanes

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Total Pages : 174 pages
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Book Synopsis Carbon-nitrogen Bond Formations Via the Stille Cross-coupling Reaction and Investigations of the Cross-coupling of Terminal Dibromoolefins with Organostannanes by : Gregory Alan Hartmann

Download or read book Carbon-nitrogen Bond Formations Via the Stille Cross-coupling Reaction and Investigations of the Cross-coupling of Terminal Dibromoolefins with Organostannanes written by Gregory Alan Hartmann and published by . This book was released on 1997 with total page 174 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Development of Novel Methods for the Formation of C-C and C-N Bonds

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Book Synopsis Development of Novel Methods for the Formation of C-C and C-N Bonds by : Christopher Andre Kalnmals

Download or read book Development of Novel Methods for the Formation of C-C and C-N Bonds written by Christopher Andre Kalnmals and published by . This book was released on 2019 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Carbon-carbon and carbon-nitrogen bonds are some of the most common motifs in organic molecules and as a result, the invention of new methods for selectively forming these bonds is highly important. The first half of this thesis describes the discovery of two novel and unexpected carbon-carbon bond forming reactions, and also includes a review on the unique chemistry of geminal and vicinal bis(sulfones). The second half of this work deals with enantioselective carbon-nitrogen bond formation, and describes the development of two transition metal-catalyzed asymmetric allylic alkylation reactions. It also contains a review on annulative allylic alkylation reactions between dual electrophiles and dual nucleophiles and their applications in complex molecule synthesis.

Transition Metal-catalyzed C-N Bond Formation Via Addition of Nitrogen Nucleophiles Towards Alkenes and Related Tandem Cyclization Reactions

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Total Pages : 498 pages
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Book Synopsis Transition Metal-catalyzed C-N Bond Formation Via Addition of Nitrogen Nucleophiles Towards Alkenes and Related Tandem Cyclization Reactions by : Dong Xing (Ph. D.)

Download or read book Transition Metal-catalyzed C-N Bond Formation Via Addition of Nitrogen Nucleophiles Towards Alkenes and Related Tandem Cyclization Reactions written by Dong Xing (Ph. D.) and published by . This book was released on 2011 with total page 498 pages. Available in PDF, EPUB and Kindle. Book excerpt: