Download or read book Defined Transition Metal Complexes for Catalytic Oxidative C N Bond Formation written by Alvaro Iglesias and published by . This book was released on 2009 with total page 210 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis deals with the development of transition metal based processes for C-N bond formation. To this end, it describes three different areas of research, the activation of azo-compounds for a concomitant aryl-amination under Pd(0)/Pd(II) catalysis, secondly, the use of gold catalysts for an oxidative diamination of alkenes led to the development of Au(I)/Au(III) catalysis. The latter process gave rise to stoichiometric experiments on the feasibility of oxidation of gold(I) complexes. This work was equally extended to investigate pathways of reductive C-N bond formation from Pd(II)-amidato complexes under oxidative conditions.
Download or read book C X Bond Formation written by Arkadi Vigalok and published by Springer. This book was released on 2010-06-30 with total page 198 pages. Available in PDF, EPUB and Kindle. Book excerpt: Contents: Kilian Muñiz: Transition Metal Catalyzed Electrophilic Halogenation of C-H bonds in alpha-Position to Carbonyl Groups; Arkadi Vigalok * and Ariela W Kaspi: Late Transition Metal-Mediated Formation of Carbon-Halogen Bonds; Paul Bichler and Jennifer A. Love*: Organometallic Approaches to Carbon-Sulfur Bond Formation; David S. Glueck: Recent Advances in Metal-Catalyzed C-P Bond Formation; Andrei N. Vedernikov: C-O Reductive Elimination from High Valent Pt and Pd Centers; Lukas Hintermann: Recent Developments in Metal-Catalyzed Additions of Oxygen Nucleophiles to Alkenes and Alkynes; Moris S. Eisen: Catalytic C-N, C-O and C-S bond formation promoted by organoactinide complexes.
Download or read book Oxidative Cross Coupling Reactions written by Aiwen Lei and published by John Wiley & Sons. This book was released on 2016-08-12 with total page 240 pages. Available in PDF, EPUB and Kindle. Book excerpt: The first handbook on this emerging field provides a comprehensive overview of transition metal-catalyzed coupling reactions in the presence of an oxidant. Following an introduction to the general concept and mechanism of this reaction class, the team of authors presents chapters on C-C cross-coupling reactions using organometallic partners, C-Heteroatom bond forming reactions via oxidative couplings, and C-H couplings via C-H activation. The text also covers such groundbreaking topics as recent achievements in the fields of C-C and C-X bond formation reactions as well as C-H activation involving oxidative couplings. With its novel and concise approach towards important building blocks in organic chemistry and its focus on synthetic applications, this handbook is of great interest to all synthetic chemists in academia and industry alike.
Download or read book Transition Metal Catalyzed Oxidative Cross Coupling Reactions written by Aiwen Lei and published by Springer. This book was released on 2018-12-14 with total page 192 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book is a comprehensive text covering the research and development trends in the booming field of transition metal catalyzed oxidative cross-coupling reactions. Oxidative cross-coupling reaction is a new method to forming chemical bonds besides the traditional cross-coupling reactions. This book provides the answers to how this coupling reaction occurs and what its advantages are. The palladium, copper and iron catalyzed oxidative cross-coupling reactions as the main focuses of interest are described in detail. The oxidative cross-coupling reactions catalyzed by other metals and transition-metal-free oxidative coupling reactions are also introduced.This book provides a useful reference source for researchers and graduates in the field of transition metal catalyzed coupling reactions. It is also valuable to researchers working in pharmaceutical companies, fine organic chemical companies, and etc.
Download or read book Density Functional Theory Studies of Selected Transition Metals Catalyzed C C and C N Bond Formation Reactions written by Xufeng Lin and published by . This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Density Functional Theory Studies of Selected Transition Metals Catalyzed C-C and C-N Bond Formation Reactions" by Xufeng, Lin, 林旭鋒, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled DENSITY FUNCTIONAL THEORY STUDIES OF SELECTED TRANSITION METALS CATALYZED C-C AND C-N BOND FORMATION REACTIONS submitted by Xufeng LIN for the degree of Doctor of Philosophy at The University of Hong Kong in September 2007 This thesis presents theoretical investigations on selected transition metals catalyzed C-C and C-N bond formation reactions. Density functional theory (DFT) calculations were performed to explore the potential energy surfaces of (1) alkyl-alkyl cross-coupling reactions catalyzed by nickel-trinitrogen ligand complexes, and (2) amidation of C-H bonds and alkene aziridinations catalyzed by rhodium and ruthenium complexes. In the first part three catalytic cycles were examined for Ni-catalyzed Negishi alkyl-alkyl cross-coupling with the ligand of 2,2'',6'',2''''-terpyridine (tpy). The catalytic cycle that involves a sequence of oxidative addition-reductive elimination- transmetalation with the actual catalyst of Ni(tpy)-CH or Ni(tpy)-I [Ni(I)] was found to be feasible, and this provide some new insight into the chemistry of metal-catalyzed cross-coupling reactions. The oxidative addition undergoes in a two-step radical pathway to produce a Ni(III) species, and the Ni(III) speices undergo reductive elimination to afford the alkyl-alkyl coupled product. Bulk solvation effect was considered in examination of this catalytic cycle. Cross-coupling reactions of both primary and secondary alkyl iodides in reactions with organozinc reagent were compared. Based on these results a Ni-catalyzed Negishi cross-coupling reaction of a secondary alkyl bromide was investigated with the ligands of bis(oxazolinyl)pyridine (Pybox). Reductive elimination step was found to be irreversible and rate-determining in generating the coupled product. When Pybox is replaced (S)-(i-Pr)-Pybox with C symmetry, it was found that the racemic 1-bromoindane can be converted into the coupled product in S enantiomer with high enantioselectivity. This is accounted for higher free energy of activation needed for the reductive elimination step in generating the R enantiomer compared to the S enatiomer in the case of (S)-(i-Pr)-Pybox ligand. In the second part the intramolecular amidation of C-H bonds in carbamates and sulfonamate esters were examined with dirhodium tetracarboxylate [Rh(II)] as the catalyst. "Rh(II)-nitrene" complexes were found to be largely favorable in free energy compared to the staring materials or the "Rh(II)-phenyliodinane" complexes. The singlet and triplet states of a Rh(II)-nitrene complex are very close in energy, which was attributed to the π-π orbital interaction of nitrene and Rh. However, a singlet Rh(II)- nitrene undergoes C-H bond cleavage accompanied by N-H and C-N bond formation in a concerted pathway, whereas a triplet Rh(II)-nitrene undergoes C-H bond cleavage accompanied by only N-H formation to produce a biradical. A singlet pathway is favorable over its corresponding triplet pathway in free energy of activation. Rh(II)- catalyzed nitrene insertion into a C=C double bond in competition with insertion into a C-H bond was also examined with the unsaturated substrate of sulfonamate esters. Similar cases were found for the reaction systems in which intramolecular amidation of C-H bonds in the cyclohexane ring in a sulfamate ester is catalyzed by Ru-porphyrins. In all these catalytic systems, stereoselectiviti
Download or read book C C Bond Activation written by Guangbin Dong and published by Springer. This book was released on 2014-09-18 with total page 265 pages. Available in PDF, EPUB and Kindle. Book excerpt: The series Topics in Current Chemistry presents critical reviews of the present and future trends in modern chemical research. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience. Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field. Review articles for the individual volumes are invited by the volume editors. Readership: research chemists at universities or in industry, graduate students
Download or read book C H Activation for Asymmetric Synthesis written by Françoise Colobert and published by John Wiley & Sons. This book was released on 2019-11-11 with total page 294 pages. Available in PDF, EPUB and Kindle. Book excerpt: Provides, in one handbook, comprehensive coverage of one of the hottest topics in stereoselective chemistry Written by leading international authors in the field, this book introduces readers to C-H activation in asymmetric synthesis along with all of its facets. It presents stereoselective C-H functionalization with a broad coverage, from outer-sphere to inner-sphere C-H bond activation, and from the control of olefin geometry to the induction of point, planar and axial chirality. Moreover, methods wherein asymmetry is introduced either during the C-H activation or in a different elementary step are discussed. Presented in two parts?asymmetric activation of C(sp3)-H bonds and stereoselective synthesis implying activation of C(sp2)-H bonds?CH-Activation for Asymmetric Synthesis showcases the diversity of stereogenic elements, which can now be constructed by C-H activation methods. Chapters in Part 1 cover: C(sp3)-H bond insertion by metal carbenoids and nitrenoids; stereoselective C-C bond and C-N bond forming reactions through C(sp3)?H bond insertion of metal nitrenoids; enantioselective intra- and intermolecular couplings; and more. Part 2 looks at: C-H activation involved in stereodiscriminant step; planar chirality; diastereoselective formation of alkenes through C(sp2)?H bond activation; amongst other methods. -Covers one of the most rapidly developing fields in organic synthesis and catalysis -Clearly structured in two parts (activation of sp3- and activation of sp2-H bonds) -Edited by two leading experts in C-H activation in asymmetric synthesis CH-Activation for Asymmetric Synthesis will be of high interest to chemists in academia, as well as those in the pharmaceutical and agrochemical industry.
Download or read book New Reactivity and Selectivity in Transition Metal catalyzed C C and C N Bond Forming Processes written by and published by . This book was released on 2015 with total page 881 pages. Available in PDF, EPUB and Kindle. Book excerpt: Part I. Palladium-Catalyzed Carbon-Carbon Bond Forming Cross-Couplings Chapter 1. Ligand-Controlled Palladium-Catalyzed Regiodivergent Suzuki-Miyaura Cross-Coupling of Allylboronates and Aryl Halides An orthogonal set of catalyst systems based on the use of two biarylphosphine ligands has been developed for the Suzuki-Miyaura coupling of 3,3-disubstituted and 3-monosubstituted allylboronates with (hetero)aryl halides. These methods allow for the regiodivergent preparation of either the ct- or the [gamma]-isomeric coupling product with high levels of site selectivity using a common allylboron building block. Preliminary investigations have demonstrated the feasibility of an enantioselective variant for the [gamma]-selective cross-coupling using chiral monodentate biarylphosphine ligands. Chapter 2. Palladium-Catalyzed Completely Linear-Selective Negishi Coupling of 3,3-Disubstituted Organozinc Reagents with Aryl and Vinyl Electrophiles A palladium-catalyzed general and completely linear-selective Negishi coupling of 3,3- disubstituted allyl organozinc reagents with (hetero)aryl and vinyl electrophiles has been developed. This method provided an effective means for accessing highly functionalized aromatic and heteroaromatic compounds bearing prenyl-type side chains. The utility of the current protocol was further illustrated in the concise synthesis of the anti-HIV natural product siamenol. Chapter 3. Palladium-Catalyzed Highly Selective Negishi Cross-Coupling of Secondary Alkylzinc Reagents with Aryl and Heteroaryl Halides The palladium-catalyzed Negishi cross-coupling of secondary alkylzinc reagents and heteroaryl halides with high levels of regioisomeric retention has been described. The development of a series of biarylphosphine ligands has led to the identification of an improved catalyst for the coupling of electron-deficient heterocyclic substrates. Preparation and characterization of oxidative addition complex (L)Pd(Ar)(Br) provided insight into the unique reactivity of palladium catalysts based on CPhos-type biarylphosphine ligands in facilitating challenging reductive elimination processes. Chapter 4. Mechanistic Studies on the Aryl-Trifluoromethyl Reductive Elimination from Pd(II) Complexes Based on Biarylphosphine Ligands A series of monoligated (L)Pd(Ar)(CF3) (L = dialkyl biarylphosphine) have been prepared and studied in an effort to shed light on the mechanism of the aryl-trifluoromethyl reductive elimination from these systems. Combined experimental and computational investigations revealed unique reactivity and binding modes of (L)Pd(Ar)(CF3) complexes derived from BrettPhos-type biarylphosphines. In contrast to a variety of C-C and C-heteroatom bond forming reductive eliminations, kinetic measurements showed this Ar-CF3 reductive elimination is largely insensitive to the electronic nature of the to-be-eliminated aryl substituent. Furthermore, the aryl group serves as the nucleophilic coupling partner in this reductive elimination process. The structure-reactivity relationship of biarylphosphine ligands was also investigated, uncovering distinct roles of the ipso-arene and alkoxy interactions in affecting these reductive elimination reactions. Part II. Copper-Catalyzed Carbon-Carbon and Carbon-Nitrogen Bond Formation via Olefin Functionalization Chapter 5. Copper-Catalyzed ortho C-H Cyanation of Vinylarenes A copper-catalyzed regioselective ortho C-H cyanation of vinylarenes has been developed. This method provides an effective means for the selective functionalization of vinylarene derivatives. A copper-catalyzed cyanative dearomatization mechanism is proposed to account for the regiochemical course of this reaction. This mechanism has been validated through density functional theory calculations. Computational studies revealed that the high level of ortho selectivity in the electrophilic cyanation event originates from a unique six-membered transition state that minimizes unfavorable steric repulsions. Chapter 6. Regio- and Stereospecific 1,3-Allyl Group Transfer Triggered by a Copper-Catalyzed Borylation/ortho-Cyanation Cascade A copper-catalyzed borylation/cyanation/allyl group transfer cascade has been developed. This process features an unconventional copper-catalyzed electrophilic dearomatization followed by the subsequent regio- and stereospecific 1,3-transposition of the allyl fragment enabled by the aromatization-driven Cope rearrangement. This method provides an effective means for the construction of adjacent tertiary and quaternary stereocenters with high levels of stereochemical purity. Chapter 7. Copper-Catalyzed Asymmetric Hydroamination of Unactivated Internal Olefins: an Effective Means to Access Highly Enantioenriched Aliphatic Amines Catalytic assembly of enantiopure aliphatic amines from abundant and readily available precursors has long been recognized as a paramount challenge in synthetic chemistry. We describe a mild and general copper-catalyzed hydroamination that effectively converts unactivated internal olefins-an important yet unexploited class of abundant feedstock chemicals-into highly enantioenriched [alpha]-branched amines (>/= 96% ee) featuring two minimally differentiated aliphatic substituents. This method provides a powerful means to access a broad range of advanced, highly functionalized enantioenriched amines of interest in pharmaceutical research and other areas.
Download or read book Transition Metals in Coordination Environments written by Ewa Broclawik and published by Springer. This book was released on 2019-03-16 with total page 532 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book focuses on the electronic properties of transition metals in coordination environments. These properties are responsible for the unique and intricate activity of transition metal sites in bio- and inorganic catalysis, but also pose challenges for both theoretical and experimental studies. Written by an international group of recognized experts, the book reviews recent advances in computational modeling and discusses their interplay using experiments. It covers a broad range of topics, including advanced computational methods for transition metal systems; spectroscopic, electrochemical and catalytic properties of transition metals in coordination environments; metalloenzymes and biomimetic compounds; and spin-related phenomena. As such, the book offers an invaluable resource for all researchers and postgraduate students interested in both fundamental and application-oriented research in the field of transition metal systems.
Download or read book Earth Abundant Transition Metal Catalyzed Reactions written by and published by Elsevier. This book was released on 2024-09-18 with total page 270 pages. Available in PDF, EPUB and Kindle. Book excerpt: Earth-Abundant Transition Metal Catalyzed Reactions, Volume 74 in the Advances in Catalysis series, highlights new advances in the field, with this new volume presenting interesting chapters. Each chapter is written by an international board of authors. Chapters in this new release include in Chiral Iron Complexes for Asymmetric Catalysis, Recent advances in Ni-catalyzed Functionalization of Strong C-O and C-H Bonds, Low-valent Molecular Cobalt Complexes for Reductive Chemistry, Iron-catalyzed group-transfer reactions with hypervalent iodine reagents, and Iron Porphyrins for Mediating Atom Efficient C–C Bond Formations. Provides the authority and expertise of leading contributors from an international board of authors Presents the latest release in Advances in Catalysis serials Updated release includes the latest information in the field
Download or read book Cleavage of Carbon Carbon Single Bonds by Transition Metals written by Masahiro Murakami and published by John Wiley & Sons. This book was released on 2015-12-21 with total page 292 pages. Available in PDF, EPUB and Kindle. Book excerpt: Edited by leading experts and pioneers in the field, this is the first up-to-date book on this hot topic. The authors provide synthetic chemists with different methods to activate carbon-carbon sigma bonds in organic molecules promoted by transition metal complexes. They explain the basic principles and strategies for carbon-carbon bond cleavage and highlight recently developed synthetic protocols based on this methodology. In so doing, they cover cleavage of C-C bonds in strained molecules, reactions involving elimination of carbon dioxide and ketones, reactions via retroallylation, and cleavage of C-C bonds of ketones and nitriles. The result is an excellent information source for researchers in academia and industry working in the field of synthetic organic chemistry, while equally serving as supplementary reading for advanced courses in organometallic chemistry and catalysis.
Download or read book Pincer Compounds written by David Morales-Morales and published by Elsevier. This book was released on 2018-04-11 with total page 756 pages. Available in PDF, EPUB and Kindle. Book excerpt: Pincer Compounds: Chemistry and Applications offers valuable state-of-the-art coverage highlighting highly active areas of research—from mechanistic work to synthesis and characterization. The book focuses on small molecule activation chemistry (particularly H2 and hydrogenation), earth abundant metals (such as Fe), actinides, carbene-pincers, chiral catalysis, and alternative solvent usage. The book covers the current state of the field, featuring chapters from renowned contributors, covering four continents and ranging from still-active pioneers to new names emerging as creative strong contributors to this fascinating and promising area. Over a decade since the publication of Morales-Morales and Jensen’s The Chemistry of Pincer Compounds (Elsevier 2007), research in this unique area has flourished, finding a plethora of applications in almost every single branch of chemistry—from their traditional application as very robust and active catalysts all the way to potential biological and pharmaceutical applications. Describes the chemistry and applications of this important class of organometallic and coordination compounds Includes contributions from global leaders in the field, featuring pioneers in the area as well as emerging experts conducting exciting research on pincer complexes Highlights areas of promising and active research, including small molecule activation, earth abundant metals, and actinide chemistry
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 Transition Metal Catalyzed C N Bond Formation Via Addition of Nitrogen Nucleophiles Towards Alkenes and Related Tandem Cyclization Reactions written by Dong Xing and published by Open Dissertation Press. This book was released on 2017-01-26 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Transition Metal-catalyzed C-N Bond Formation via Addition of Nitrogen Nucleophiles Towards Alkenes and Related Tandem Cyclization Reactions" by Dong, Xing, 邢栋, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. DOI: 10.5353/th_b4658915 Subjects: Ring formation (Chemistry) Transition metal catalysts Polycyclic compounds - Synthesis
Download or read book Cleavage of Carbon Carbon Single Bonds by Transition Metals written by Masahiro Murakami and published by John Wiley & Sons. This book was released on 2015-09-21 with total page 296 pages. Available in PDF, EPUB and Kindle. Book excerpt: Edited by leading experts and pioneers in the field, this is the first up-to-date book on this hot topic. The authors provide synthetic chemists with different methods to activate carbon-carbon sigma bonds in organic molecules promoted by transition metal complexes. They explain the basic principles and strategies for carbon-carbon bond cleavage and highlight recently developed synthetic protocols based on this methodology. In so doing, they cover cleavage of C-C bonds in strained molecules, reactions involving elimination of carbon dioxide and ketones, reactions via retroallylation, and cleavage of C-C bonds of ketones and nitriles. The result is an excellent information source for researchers in academia and industry working in the field of synthetic organic chemistry, while equally serving as supplementary reading for advanced courses in organometallic chemistry and catalysis.
Download or read book Regioselective Carbon nitrogen Bond Formation Via Oxidative Transition Metal Catalysis written by Louis Marchetti and published by . This book was released on 2015 with total page 346 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Catalysis written by B. Viswanathan and published by CRC Press. This book was released on 2002 with total page 428 pages. Available in PDF, EPUB and Kindle. Book excerpt: Students contemplating careers in chemistry, whether in research, practice, or academia, obviously need a solid grounding in proper research methodology, reasoning, and analysis. However, there are few resources available that efficiently and effectively introduce these concepts and techniques and inspire students to undertake advanced research, particularly in the area of catalysis. Catalysis: Principles and Applications evolved out of a special, resoundingly successful short course for graduate students interested in catalysis. It covers nearly the entire gamut of the subject, from its fundamentals to its modern, applied aspects. The chapters were contributed by catalysis specialists from leading academic institutions, national laboratories and industrial R&D labs. Because they are based on the authors' lecture notes, each chapter is highly accessible and for the most part self-contained. Topics include various spectroscopic methods, biocatalysis, x-ray and thermal analysis, photocatalysis, and recent developments, such as solid acid catalysts, fine chemical synthesis, and computer-aided catalyst design. The book also contains discussions on a variety of modern applications, including environmental pollution control, petroleum refining, fuel cells, and monomolecular films. Logically presented, well-illustrated, and thoroughly referenced, Catalysis: Principles and Applications offers an outstanding basis for courses in catalysis. It not only imparts the fundamentals, synthesis, characterization, and applications of catalysis, but does so in a way that will motivate students to pursue more advanced studies and ultimately careers in the field.
