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1
Henderson, William Howell. "Palladium-Mediated C-H Activations". The Ohio State University, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=osu1318003095.
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Chudasama, V. "The use of aerobic aldehyde C-H activation for the construction of C-C and C-N bonds". Thesis, University College London (University of London), 2011. http://discovery.ucl.ac.uk/1324525/.
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This thesis describes a series of studies directed towards the use of aerobic aldehyde C-H activation for the construction of C-C and C-N bonds by the process of hydroacylation. Chapter 1 provides an introduction to the research project and an overview of strategies for hydroacylation. Chapter 2 describes the application of aerobic aldehyde C-H activation for the hydroacylation of vinyl sulfonates and sulfones. A discussion on the mechanism of the transformation, the effect of using aldehydes with different oxidation profiles and the application of chiral aldehydes is also included. Chapter 3 describes the functionalisation of γ-keto sulfonates with particular emphasis on an elimination/conjugate addition strategy, which provides an indirect approach to the hydroacylation of electron rich alkenes. Chapters 4 and 5 describe the application of aerobic aldehyde C-H activation towards the hydroacylation of α,β-unsaturated esters and vinyl phosphonates, respectively. An in-depth discussion on the mechanism and aldehyde tolerance of each transformation is also included. Chapter 6 describes acyl radical approaches towards C-N bond formation with particular emphasis on the synthesis of amides and acyl hydrazides.
3
Akhbar, A. R. "Hydroacylation of N=N bonds via aerobic C-H activation of aldehydes, and reactions of the products thereof". Thesis, University College London (University of London), 2014. http://discovery.ucl.ac.uk/1456292/.
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The development of methods to construct new chemical bonds efficiently and selectively whilst minimising energy usage and waste production is of high importance in organic chemistry. Many current methods employ inefficient, costly and often toxic multi step protocols to generate new chemical bonds. The hydroacylation reaction is one method of reducing such inefficiencies. The development of an aerobic hydroacylation protocol in the Caddick group has recently allowed the functionalisation of aldehydes with a wide array of electron deficient alkenes. This process relies on trapping an acyl radical intermediate, from the auto-oxidation of aldehydes to acids, with a suitable alkene. Since aldehyde auto-oxidation takes place readily in the presence of atmospheric oxygen, the aerobic hydroacylation reaction can be conducted in aqueous media in the absence of any additional reagents. Following on from previous work in the group, this thesis describes studies towards expanding the scope of this novel methodology in the formation of C-N bonds. It also assesses the scalability of this reaction in order to make acyl hydrazides for further chemical transformations; as such, the development of protocols for the conversion of acyl hydrazides to carboxylic acid derivatives and to ketones will also be described. Chapter 1 provides an introduction to and a general overview of current methods of hydroacylation and acid derivative syntheses. Chapter 2 describes the development of conditions for, and application of aerobic hydroacylation towards C N bond formation, and the scalability of the hydroacylation reaction. Chapter 3 will focus on solving the failures of previous attempts for the conversion of acyl hydrazides to tertiary amides. Chapter 4 will demonstrate the applicability of acyl hydrazides to the synthesis of carboxylic esters and describe some of its limitations. Finally, chapter 5 will reveal acyl hydrazides as a new class of precursors for the chemoselective synthesis of ketones.
4
Weeks, Amanda. "C-H activation in organic synthesis". Thesis, University of Bristol, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.535205.
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Doyle, Claire Marie. "C-H activation reactions of tetrahydropyridines". Thesis, Imperial College London, 2012. http://hdl.handle.net/10044/1/9469.
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This thesis is presented as five chapters: Chapter 1.0 is divided into two sections: the first is a review of palladium-catalysed C–C bond forming reactions. It covers palladium-catalysed cross-coupling reactions; C–H bond functionalisation; the Heck reaction and functionalisation of heteroaromatic C–H bonds. Secondly the use of tetrahydropyridines in organic synthesis is discussed, with a particular focus on methodology developed by the Craig group. Chapter 2.0 discusses the research carried out during this studentship. It is divided into six sections and discusses the results obtained from research efforts into: our initial strategy for tetrahydropyridine synthesis; an SN1 approach; an α,β-unsaturated lactam approach; synthesis of 3-methoxy aryl-substituted tetrahydropyridines; synthesis of heteroaromatic analogues and further elaboration of tricyclic tetrahydropyridines. Chapter 3.0 details future work proposed within the areas described above. Chapter 4.0 details the experimental procedures employed and spectroscopic data for the compounds discussed in chapter 2.0. Finally, chapter 5.0 lists the references sourced in this thesis.
6
Vastine, Benjamin Alan. "Understanding mechanisms for C-H bond activation". [College Station, Tex. : Texas A&M University, 2008. http://hdl.handle.net/1969.1/ETD-TAMU-2679.
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Khamker, Qudsia. "Ambiphilic C-H activation routes to heterocycles". Thesis, University of Leicester, 2014. http://hdl.handle.net/2381/28919.
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This thesis describes investigations of Cp*Rh- and (p-Cy)Ru-catalysed C-H functionalisation reactions of various substrates with alkynes and alkenes for the formation of several heterocycles and carbocycles. Mechanistic studies and DFT calculations are also presented. Chapter One includes a discussion of different mechanisms of C-H activation namely oxidative addition, σ-bond metathesis, 1,2-addition, electrophilic activation and AMLA/CMD. The applications of these different mechanisms of C-H activation in catalysis are also discussed with a particular emphasis on the use of AMLA/CMD in direct arylation reactions. Chapter Two gives an overview of stoichiometric and catalytic studies of AMLA C-H activation and subsequent reactivity with alkynes at Ir, Rh, and Ru. The results of Cp*Rh- and some (p-Cy)Ru-catalysed reactions of C-phenylpyrazoles with alkynes are presented. N-H and C-H activation occurs, leading to heterocycles. Mechanistic studies and DFT calculations show that C-H activation is reversible and rate limiting in the cases examined. Chapter Three is similar to Chapter Two but focusses on reactions with alkenes. The Cp*Rh-catalysed reactions of C-phenylpyrazoles with alkenes lead to mono or divinyl products which may undergo further aza-Michael cyclisations if the alkene is a good Michael acceptor. Mechanistic studies and DFT calculations are also discussed. Chapter Four deals with Cp*Rh-catalysed coupling reactions of other directing groups, including imidazole, imidazoline, pyrazolidinone, hydrazine, carboxylic acid and oxime with alkynes. Again, there is discussion on the different factors affecting product selectivity. Chapter Five gives a summary of all the conclusions on the work presented in this thesis. Throughout the thesis, all new compounds are characterised spectroscopically and several compounds have been characterised by X-ray crystallography.
8
Wiley, Jack Scott. "C-H bond activation in iridium complexes /". Thesis, Connect to this title online; UW restricted, 1999. http://hdl.handle.net/1773/8510.
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Bu, Qingqing. "Ruthenium- and Cobalt-Catalyzed C-H Activation". Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2018. http://hdl.handle.net/11858/00-1735-0000-002E-E4FC-F.
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Moselage, Marc Philipp. "C-H and C-C Activation by Cobalt and Ruthenium Catalysis". Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2017. http://hdl.handle.net/11858/00-1735-0000-0023-3FB2-6.
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11
Torkelson, Jeffrey Robert. "C-H bond activation and C-C bond formation at adjacent metals". Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp03/NQ34848.pdf.
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12
Chow, Catherine. "C-H activation by a tungsten trimethylsilylallyl complex". Thesis, University of British Columbia, 2012. http://hdl.handle.net/2429/42646.
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Thermolysis of Cp*W(NO)(Np)(η³-CH₂CHCHSiMe₃) generates a 16-electron allene
intermediate complex that selectively activates hydrocarbons at their methyl groups. In the
case of linear alkanes, only terminal activation is observed. This selectivity persists in the
presence of an ether functionality, but not of other oxygen-containing substrates such as
aldehydes and alcohols. With these latter substrates, oxidation of the complex to
Cp*W(O)₂Np has been noted. The existence of the allene intermediate has been verified by
two thermolytic experiments, and kinetic studies show that Cp*W(NO)(Np)(η³-
CH₂CHCHSiMe₃) is consumed according to pseudo-first-order kinetics during C–H bond
activation. The neopentyl ligand can be functionalized by reaction with CO, and the resulting
acyl complexes undergo chemical exchange on a slow timescale. The congeneric Mo
complex has also been synthesized, and although this complex is equally capable of
generating the η²-allene intermediate, its preferred mode of reactivity is coupling of the allyl
and alkyl ligands. As a result, the Mo complex is inferior to the W system for C–H
activation.
The thermolysis of Cp*W(NO)(Np)(η³-CH₂CHCHSiMe₃) in benzene has been
studied since the major products of this reaction each contain a 1,3-disubstituted allyl ligand
which might reduce reactivity at the allyl ligand in subsequent chemistry. In thermolytic
conditions, the resulting disubstituted allyl hydride complex undergoes no apparent reaction
with alkanes, but with deuterobenzene, deuterium incorporation into the allyl ligand is
observed. In addition to H/D exchange, the hydride ligands in these complexes can also migrate onto the allyl ligand, forming an η²-olefin complex that can be trapped as the
pyridine adduct.
The activation of fluorobenzenes by Cp*W(NO)(Np)(η³-CH₂CHCHSiMe₃) was also
studied, and in these substrates, exclusive activation of the C–H bond is observed. Migration
of the newly formed aryl ligands onto the allyl ligand does not occur when there is a fluorine
atom in the ortho position, which is probably due to the reduced nucleophilicity of the ligand
relative to the unfluorinated phenyl ligand. Selectivity in the activation of C–H bonds in
fluorobenzenes appears to be determined by sterics.
13
Luo, Junfei. "Controlling regioselectivity and enantioselectivity in C-H activation". Thesis, Queen Mary, University of London, 2015. http://qmro.qmul.ac.uk/xmlui/handle/123456789/9550.
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The direct functionalisation of C-H bonds has emerged in recent years as an efficient and atom-economic alternative to the traditional cross coupling reaction. One of the challenges towards this goal is the selective transformation of a particular C-H bond amongst many other C-H bonds. This thesis describes studies on the use of CO2 as a traceless promoter for controlling meta-regioselective arylation of phenols and a separate investigation into an enantioselective arylation of pre-chiral η6-arene tricarbonyl chromium complexes. The introduction provides a general review of recent advances in the use of coordinating moieties as directing groups for selective activation of aromatic C-H bonds. The challenge of meta-selective C-H activation and the direct functionalisation of phenols is assessed and discussed. To overcome the scarce methods for accessing meta-arylated phenols, our objective was to develop an efficient methodology for the meta-arylation of phenols. Our strategy includes an ortho-carboxylation of the phenol followed by ortho-arylation of the salicylic acids and the subsequent protodecarboxylation to afford meta-arylphenols is proposed. A step-wise approach towards our aim is applied. First, a convenient and efficient method for the carboxylation of phenols is presented in Chapter 2. Then, a tandem arylation/decarboxylation reaction of salicylic acids is described in Chapter 3. Last, an efficient methodology for the meta-arylation of phenols via carboxylation/arylation/ decarboxylation processes in one-pot is presented in the following section in Chapter 3. To demonstrate the utility of this powerful methodology, an efficient synthesis of γ-secretase inhibitor and the further transformation of the meta-arylphenols are shown. Furthermore, an alternative method is described for the synthesis of meta-arylphenols via a tandem oxidation/arylation/decarboxylation reaction of salicylaldehydes. In Chapter 4, an approach towards the development of enantioselective C-H arylation leading to planar chirality is stated. Preliminary results are presented for this ongoing project.
14
Müller, Thomas. "C-H Activation by Nickel and Iron Catalysis". Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2019. http://hdl.handle.net/21.11130/00-1735-0000-0003-C189-8.
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Gao, Longhui. "C-H bond activation catalyzed by Ruthenium nanoparticles". Thesis, Université Paris-Saclay (ComUE), 2017. http://www.theses.fr/2017SACLS348/document.
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Les molécules marquées par des isotopes de l’hydrogène possèdent de nombreuses applications dans divers domaines tels que la chimie, la biologie ou en science des matériaux. Dans le domaine de la recherche de nouveaux médicaments, les études liées à la pharmacocinétique nécessitent un accès rapide à des molécules marquées afin de ne pas impacter les coûts et les délais de développement. Le développement de la métabolomique a aussi entrainé une augmentation du besoin en molécules marquées isotopiquement. En effet, les molécules deuterées peuvent être utilisées en tant qu’étalons internes pour la quantification rapide des métabolites présents dans des tissus ou des fluides biologiques. La première partie de cette thèse concerne le développement d’une méthode générale de marquage de motifs de type thioéther dans des molécules complexes à l’aide d’une nouvelle réaction d’échange isotopique (catalysée par des nanoparticules de Ruthénium). D’un point de vue fondamental cette transformation représente le premier exemple de (Csp³)-H activation dirigée par un atome de soufre. En termes d’application, cette nouvelle réaction permet la synthèse rapide d’étalons internes pour la quantification LC-MS/MS et le marquage tritium de molécules complexes. La seconde partie de cette thèse relate le développement d’une nouvelle méthode d’homocouplage de phénylpyridines catalysée par Ru/C. Différents substrats comportant des substituants riches et pauvres en électron ont été couplés avec de bons rendements. Ces dimères ont ensuite été utilisés pour synthétiser de nouveaux complexes de bore dont les propriétés photophysiques ont été étudiées. Dans une troisième partie, la mise au point d’une réaction palladocatalysée permettant d’obtenir des molécules polycycliques contenant un motif de type pyridine est développéeDeuterated and tritiated compounds are widely used in numerous applications in chemistry, biology and material science. In the drug discovery and development process, ADME studies require quick access to labelled molecules, otherwise the drug development costs and timeline are significantly impacted. The rapid development of metabolomics has also increased the need for isotopically labelled compounds. In particular, deuterated molecules are used as internal standards for quantitative LC-MS/MS analysis of metabolites in biological fluids and tissues. In this context, a general method allowing the deuterium and tritium labelling of bioactive thioethers using a HIE reaction is described in the first chapter. From a fundamental point of view, this transformation is the first example of (Csp³)-H activation directed by a sulfur atom. In terms of application, this new reaction has been proved to be useful for the preparation of deuterated LC-MS/MS reference materials and tritiated pharmaceuticals owning high specific activity.In the second chapter of this manuscript, the development of a method allowing the cross-dehydrogenative homocoupling of 2-arylpyridines catalyzed by Ru/C is developed. Various substrates with different substituents were efficiently coupled to give the desired dimers in good yield. In terms of application, a series of pyridine-boron complexes derived from the phenyl pyridine dimers were also synthesized and their photophysical properties were studied.In the third chapter, a regioselective palladium catalyzed intramolecular arylation reaction allowing the synthesis of pyridine containing polycyclic compounds is described
16
Wang, Hui. "Cobalt(III)- and Manganese(I)-Catalyzed C-H and C-C Activations". Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2019. http://hdl.handle.net/11858/00-1735-0000-002E-E5EF-5.
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Liu, Weiping. "Ruthenium- and Manganese-Catalyzed C−O and C−C Formation via C−H Activation". Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2016. http://hdl.handle.net/11858/00-1735-0000-0028-8771-3.
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Raghuvanshi, Keshav. "Ruthenium(II)-Catalyzed C-N, C-O and C-C Formations by C-H Activation". Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2017. http://hdl.handle.net/11858/00-1735-0000-002B-7D4C-2.
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Bowen, John George. "C-H activation in the formation of C-N and C-O Bonds". Thesis, University of Bristol, 2015. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.685335.
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The regioselective activation of C-H bonds and subsequent transformation into desirable functional groupS is an attractive prospect in organic synthesis. We have developed two novel C-H functionalisation reactions; the first is an intramolecular, sulfonamide directed, C-H amination reaction for the synthesis of 3_phenylisoindolinone derivates and the second is a sulfonamide directed ortho C-H acetoxylation reaction. Both isoindolinones and phenol derivatives of sulfonamides are important motifs in numerous pharmaceutically relevant compounds. The Cull-catalysed intramolecular C-H amination reaction for the synthesis of substituted 3-phenylisolindolinone derivatives (Scheme i) was found to be tolerant to substitution on both aromatic rings, however, no reaction was observed on exchanging the tethered aryl group for an alkyl group. Mechanistic investigations revealed that C-H cleavage was not part of the rate-determining step which is likely to be coordination of the copper catalyst to the sulfonyl amide. Substitution of the tethered phenyl ring (R2 ) and a subsequent Hammett analysis indicated that this coordination may be accelerated by a cation-IT interaction between CU11 and the pie system of the aryl group.
20
Ho, Kelvin. "Rapid increase of molecular complexity through C–H and C–C bond activation". Thesis, University of Liverpool, 2014. http://livrepository.liverpool.ac.uk/2006222/.
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The activation of carbon-hydrogen (C–H) and carbon-carbon (C–C) bonds by transition metal catalysts is an attractive strategy to streamline organic synthesis. Herein this manuscript, the two main areas of research are described. Firstly, it was found that a nickel catalyst can promote the insertion of alkynes into the C–C bond of 3-azetidinones and 3-oxetanones to enable quicker access to pyranones and pyridinones in high yields and excellent regioselectivity. Secondly, a rhodium-catalysed pyridine directed C–H bond activation enables the rearrangement of 1,6-heptadienes into bicyclo[2.2.1]heptanes in good yields. Importantly, three stereogenic centres are created with complete diastereocontrol in this atom-efficient reaction. In chapter 1, an overview of the literature on transition metal-catalysed C–C bond activation of four membered rings is described. In chapter 2, our efforts to optimise the catalytic conditions and build the scope of the nickel-catalysed reaction are reported. In chapter 3, the results of the mechanistic investigations of the nickel-catalysed reaction are reported. Finally in chapter 4, a brief overview of the transition metal-catalysed functionalisation of an alkene C–H bond with another alkene is described. Subsequently, the optimisation of the catalytic conditions and the scope of the diastereoselective carbocyclisation of 1,6-heptadienes triggered by rhodium-catalysed activation of an alkene C–H bond are reported.
21
Korvorapun, Korkit. "Site-Selectivity in Ruthenium-Catalyzed C–H and C–C Activations". Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2020. http://hdl.handle.net/21.11130/00-1735-0000-0005-148C-7.
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Macdonald, Margaret G. Templeton J. L. "Hydrocarbon C-H activation with Tp[prime]Pt complexes". Chapel Hill, N.C. : University of North Carolina at Chapel Hill, 2007. http://dc.lib.unc.edu/u?/etd,788.
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Thesis (Ph. D.)--University of North Carolina at Chapel Hill, 2007.Title from electronic title page (viewed Dec. 18, 2007). " ... in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry." Discipline: Chemistry; Department/School: Chemistry. On t.p., [prime] is the mathematical symbol.
23
Boutadla, Youcef. "Acetate-assisted C-H activation : mechanism, scope and applications". Thesis, University of Leicester, 2010. http://hdl.handle.net/2381/8592.
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This thesis describes mechanistic investigations of acetate assisted C-H activation, the synthesis of cyclometallated complexes containing nitrogen donor ligands via this method and the applications of cyclometallated complexes in terms of insertion reactions. Chapter one introduces the synthesis, by C-H activation, of cyclometallated complexes containing C,N bidentate ligands of palladium, ruthenium, rhodium and iridium. The introduction also gives an overview on the mechanisms of C-H activation and the applications of C-H activation in catalysis, particularly in direct arylation. Chapter two provides an introduction to the synthesis of arene ruthenium and Cp*M (M = Ir, Rh) half sandwich cyclometallated complexes). The scope of cyclometallation via acetate- assisted C-H activation with different directing groups (pyrazole, pyridine, imines, imidazole, oxazoline and triazole) is discussed. The methodology is extended to six membered rings, non aromatic sp2 and sp3 C-H bonds. Mechanistic investigations using bidentate ligands showed that chelating ligands can prevent the C-H activation process. Chapter three describes a joint computational and experimental study of the cyclometallation reactions of dimethylbenzylamine (DMBA) with [IrC12Cp*]2 using a range of chelating bases. DFT calculations show that facile C-H bond cleavage occurs via 'ambiphilic metal ligand activation' (AMLA) and the ease of C-H activation is governed by the accessibility of the K2-xl base displacement step; thus, more weakly coordinating bases promote C-H activation. Chapter four reports the reactivity of cyclometallated half-sandwich complexes (synthesised in chapter two). Alkynes are shown to insert into the M-C bond. In some cases C-N bond formation occurs to form a heterocycle. The product formed depends on the ease of the reductive elimination step. The relevance of these results to the catalytic synthesis of hetero-and carbocycles is discussed. Throughout the thesis all new compounds are fully characterised spectroscopically and by elemental analysis and several compounds have been structurally characterised by X-ray crystallography.
24
Ravetz, Megan Sarah. "Effect metal electron density on C-H activation reactions". Thesis, University of Salford, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.360458.
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Fowles, E. H. "Transition metal multihydrides and aspects of C-H activation". Thesis, University of Leeds, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.233726.
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Fan, Cheng. "Dichloroboryls, diboration and C-H activation with platinum complexes". Thesis, University of Bristol, 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.443267.
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Ren, Xinkun. "A P450 BM3 toolkit for C-H activation synthesis". Thesis, University of Oxford, 2016. https://ora.ox.ac.uk/objects/uuid:1a41b822-3ba6-4116-af79-ad268e382a95.
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Cytochrome P450s are a superfamily of haem-dependent enzymes that catalyse the oxidation of natural organic compounds, most commonly via insertion of an oxygen atom from atmospheric dioxygen into a carbon-hydrogen bond. Since there is widespread interest in the selective functionalisation of C-H bonds, P450s have been extensively studied and evolved, particularly P450BM3 from Bacillus megaterium, which is catalytically self-sufficient. In this thesis, a P450BM3 variant library has been developed based on four 'generic accelerators', which have showed enhanced activity towards a broad range of non-natural substrates such as polyaromatic hydrocarbons and terpenes. The library was refined to 48 variants based on the screening results in order to maintain diversity of substrate pocket topology for oxidising a broad coverage of organic molecules. Successful applications include drug metabolism, drug fragment diversification, synthesis of flavour and fragrance compounds, steroid oxidation, late-stage functionalisation in total synthesis, and C-H amination. Total conversion was observed in most cases with a sufficient turnover number that enabled all the products to be fully characterised by NMR and MS. Two novel P450 activities were discovered as oxidative decarboxylation of an a-hydroxy carboxylic acid and C-H amination. The substrate range and varied product profiles suggest that this enzyme library is a good basis for developing selective C-H activation catalysts while expanding the P450 catalytic repertoire to include reactions important in synthetic chemistry, potentially opening new opportunities for biocatalysis.
28
Guo, Xiangyu. "Ruthenium-catalyzed C-C bond formation via functional-group directed C-H bond activation". Thesis, McGill University, 2012. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=110570.
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AbstractRuthenium-Catalyzed C-C Bond Formation via Functional-Group Directed C-H Bond ActivationXiangyu GuoAdvisor: Prof. Chao-Jun LiMcGill UniversityThis thesis is an investigation on the formation of carbon-carbon (C-C) bonds in the presence of ruthenium catalyst.In the first part of this thesis, oxidative dehydrogenative coupling reactions for carbon-carbon (C-C) bond formation are described. A ruthenium-catalyzed dimerization of 2-phenylpyridine derivatives is demonstrated to synthesize biaryls using iron(III) chloride as the terminal oxidant. In addition, the oxidative cross coupling of arenes and cycloalkanes is also illustrated, achieving a unique para-selectivity.In the second part of the thesis, a ruthenium-catalyzed olefination via decarbonylative addition of aldehydes to terminal alkynes is described. Conjugated and isolated C=C bonds can be chemoselectively generated in two catalytic systems starting from aromatic and aliphatic aldehydes. The method provides an alternative synthesis of C=C bonds from direct C-H bond addition to triple bonds.RésuméRuthenium-Catalyzed C-C Bond Formation via Functional-Group Directed C-H Bond ActivationXiangyu GuoSuperviseur: Prof. Chao-Jun LiUniversité McGillCette thèse est le résultat de la recherche sur la formation de liaisons carbone-carbone (C-C), catalysé par le ruthénium. La première partie de cette thèse expose les résultats sur la formation de liaison carbone-carbone (C-C) par la réaction de couplage oxydant par déshydrogénation. La synthèse de composés biaryl par l'utilisation d'un catalyseur de ruthénium a permis la dimérisation des dérivés de la 2-phénylpyridine en présence de chlorure de fer (III) comme oxydant terminal. En outre, l'oxydative cross-coupling entre arènes et cycloalcanes, a montrer une notable, para-sélectivité. La seconde partie de cette thèse, décrit les résultats obtenue sur la réaction d'oléfination decarbonylative entre un aldéhyde et un alcyne vrai, catalyser par le ruthénium. En partant d'aldéhydes aromatiques ou aliphatiques et par l'utilisation de deux systèmes catalytiques, la synthèse chemioselective de double liaison C=C conjuguée ou isolée ont pu être réalisé. Cette réaction fournit ainsi, une intéressante alternative à la synthèse de doubles liaisons C=C par la directe addition de liaison C-H sur une triple liaison.
29
Sun, Zhicheng. "Computational Study of C−H/C−C Activation and Functionalization with Nitrene, Carbene and Related Complexes". Thesis, University of North Texas, 2020. https://digital.library.unt.edu/ark:/67531/metadc1752352/.
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This dissertation involves inorganic/organometallic catalysis models, in particular the functionalization of carbon-hydrogen and carbon-carbon bonds. Computational methods have been utilized to better understand the factors affecting the kinetics and thermodynamics of C−H and C−C bond activation/functionalization in this dissertation. Chapter 2 investigates methane C−H activation with a diiminopyridine nitride/nitridyl complex of 3d transition metals and main group elements via three competing pathways: 1,2-addition/[2 + 2] addition, insertion and H-atom abstraction/proton coupled electron transfer. Chapter 3 investigates a transition metal catalyzed C=C bond functionalization involving C−N bond formations to synthesize aziridines from aromatic and aliphatic alkenes. The study focuses on anionic 3d transition metal (M = Mn, Fe, Co and Ni) triphenylamide-amine complexes with nitrene active intermediates for the aziridination reactions. Chapter 4 investigates a disphenoidal Ni(II) azido complex participating in intramolecular C−H functionalization and amination via a putative Ni nitridyl intermediate and a 1,2-addition/[2 + 2] addition pathway. In Chapter 5, methane oxidative addition to the Cp*ML (Cp* = η5-C5Me5; M = Co, Rh, Ir , L = CO, PMe3) motif is compared and contrasted when the classic CO and PMe3 ligands are replaced with the cyclic alkyl(amino) carbene (CAAC) as ancillary ligands.
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Holstein, Philipp. "Enantioselective C(sp3)-H Arylation and Development of a Modular C(sp3)-H Alkenylation". Thesis, Lyon 1, 2014. http://www.theses.fr/2014LYO10286.
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Récemment, l'activation C-H catalysée par des métaux de transition est devenue un outil performant pour construire des liaisons carbone-carbone et carbone hétéroatome à partir de liaisons C-H omniprésentes dans les molécules organiques. Bien que l'activation des liaisons C-H aromatiques ait été largement étudiée ces dernières années, celle des liaisons C-H aliphatiques représente encore un domaine faiblement exploré. Notre équipe s'est depuis plusieurs années intéressée au développement méthodologique de l'activation C(sp3)-H et à son application en synthèse de produits naturels et molécules bioactives. Dans la continuité des récents travaux sur la version asymétrique de cette réaction, cette thèse décrit le développement et la synthèse de nouveaux ligands du type Binepine. Ces ligands chiraux et monodentates nous ont permis de réaliser la synthèse d'indanes chiraux possédant un centre asymétrique quaternaire, de manière hautement énantio- et diastéréosélective. Cette réaction présente comme avantages l'utilisation d'une faible charge catalytique et d'une température de réaction inférieure à 100 °C, sans aucun additif. Le champ d'application de la réaction inclut notamment l'activation des liaisons C-H d'un groupement méthylène, donnant ainsi accès à des systèmes fusionnés, tricycliques. La construction de molécules non-aromatiques via une alcénylation C-H intramoléculaire a été récemment décrite et s'avère très prometteuse pour la synthèse de produits naturels saturés. Dans la continuité de ces travaux innovants, nous avons développé la synthèse de γ-lactames à partir de bromoalcènes acycliques. Cette nouvelle réaction permet de construire de manière simple et efficace des hétérocycles a cinq chainons de façon modulaire, donnant ainsi la possibilité d'envisager des nouvelles déconnections rétrosynthétiques, complémentaires des méthodes déjà établies. Cette nouvelle méthode a pu être appliquée à la synthèse totale de l'alcaloïde marin Plakoridine A, dont la structure centrale cyclique a été synthétisée en quatre étapes avec un rendement global de 37%Recently, transition-metal-catalyzed C-H activation has emerged as a powerful tool to transform stable C-H bonds into carbon-carbon or carbon-heteroatom bonds. While the activation of aromatic C-H bonds has seen a tremendous development, less effort has been devoted to the more challenging activation of aliphatic C-H bonds. Our group has a long-standing interest in the development of C(sp3)-H activation reactions and their application in the synthesis of natural products and bioactive compounds. In line with previous efforts to develop an asymmetric C(sp3)-H activation, the herein presented work details the synthesis of new Binepine ligands. These monodentate, chiral ligands enabled us to realize a highly dia- and enantioselective C(sp3)-H activation reaction allowing the construction of chiral quaternary carbon centers. Strong points of this robust method are the low catalyst loading, the low reaction temperature and the absence of additives. The substrate scope includes the rare activation of methylene C-H bonds leading to fused tricyclic carbocycles and heterocycles. The construction of non-aromatic molecules through intramolecular C-H alkenylation was recently disclosed and has great potential for the construction of saturated natural products. Based on seminal work, we have developed the synthesis of valuable γ- lactams from acyclic bromoalkenes. This new methodology offers a powerful way to build simple, five-membered N heterocycles in a modular fashion. Notably, it enables a new retrosynthetic disconnection which is complementary to conventional approaches. Finally, we set out to showcase its utility as key step in the total synthesis of the pyrrolidine alkaloid Plakoridine A. The cyclic core structure was accessed in four steps and 37% overall yield
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Zhang, Shoukun. "Selective C–H Activation by Ruthenium(II) Carboxylate and Nickelaelectro-Catalysis". Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2021. http://hdl.handle.net/21.11130/00-1735-0000-0005-155B-E.
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Schinkel, Marvin. "Rutheniumkatalysierte Addition von nicht aktivierten C(sp²)–H- und C(sp³)–H-Bindungen an Alkene". Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2013. http://hdl.handle.net/11858/00-1735-0000-0015-A380-B.
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Roudesly, Fares. "Fonctionnalisation C-H dirigée d'hétérocycles azotés". Thesis, Sorbonne université, 2018. http://www.theses.fr/2018SORUS354.
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Ce travail de thèse a apporté sa contribution et de nouvelles connaissances dans le domaine de l’activation / fonctionnalisation C-H de noyaux azotés de type pyridine et pyrrole. D’abord, nous avons développé une méthode permettant l’allylation et l’oléfination régiosélective d’azines N-oxyde en utilisant un complexe de Pd(0) formé in situ. Le champ d’application de cette réactivité a ensuite été étudié. Des études expérimentales et des calculs DFT nous ont permis de proposer un mécanisme pour les étapes d’allylation et d’isomérisation. Nous proposons que l’étape d’activation C-H est l’étape cinétiquement déterminante du cycle catalytique et se fait selon un mécanisme de déprotonation/palladation par sphère externe. Ensuite, nous nous sommes intéressés à l’application de la réaction de Murai aux dérivés du 2- pyrrole carboxaldéhyde en utilisant un complexe de Ru(0). L’utilisation du monoxyde de carbone sous pression atmosphérique nous a permis d’obtenir les produits d’acylation en présence de différents vinylsilanes et styrènes. L’application de cette réactivité à d’autres dérivés du 2-pyrrole carboxaldéhyde est en cours d’étude au laboratoireThis thesis work has brought its contribution the field of C-H activation / functionalization of nitrogenous containing rings as pyridine and pyrrole. First, we developed a strategy for a Pd- catalyzed regioselective allylation and alkenylation of azine N-oxides. The scope of this reactivity has been studied. Experimental studies and DFT calculations allowed us to propose a mechanism for the allylation and isomerization steps. We propose that the C-H activation step is the rate determining step of the catalytic cycle, and that it takes place through an outer sphere deprotonation / palladation mechanism. Next, we applied the Murai reaction to 2-pyrrole- carboxaldehyde derivatives using a Ru(0) complex. Under an atmospheric pressure of carbon monoxide, we could obtain the acylated products in the presence of various vinylsilanes and styrenes. The application of this reactivity to other 2-pyrrole carboxaldehyde derivatives is under study in the laboratory
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Poater, Teixidor Albert. "Isomerism and C-H, C-C, O-O, C-O bond activation studies by transition metals". Doctoral thesis, Universitat de Girona, 2006. http://hdl.handle.net/10803/7939.
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Aquesta tesi és el reflex que de la cooperació entre grups experimentals i grups teòrics s'aconsegueix l'assoliment d'objectius inassolibles de forma individual. A partir de la DFT s'expliquen processos inorgànics i organometàl·lics de gran valor biològic i/o industrial. La tesi està enfocada especialment a l'estudi de complexos mononuclears i binuclears de coure, on té lloc l'activació d'enllaços C-H, C-C, i O-O. L'estudi de complexos octaèdrics de ruteni ha permès dur a terme extensos estudis isomèrics i racionalitzar les propietats espectroscòpiques dels mateixos. A més a més, estudis més puntuals respecte clusters de coure, l'estudi de la reacció de Pawson-Khand, l'estudi d'enllaços Pt-Pt en complexos trimèrics de platí, a més a més de l'estudi de la isomeria de complexos de Ni i Pt.This thesis shows that the cooperation between experimental and theoretical groups gives as a result the achievement of aims impossible working independently. From DFT calculations inorganic and organometallic problems related to great biological and industrial processes can be explained. This thesis is especially focused on the study of mononuclear and binuclear copper complexes, where a C-H, C-C, and O-O bond activation takes place. The study of octahedral ruthenium complexes has allowed carrying out isomeric studies and the rationalization of spectroscopic properties. Furthermore, other little studies related to copper clusters, the Pawson-Khand reaction, Pt-Pt bond interaction in trimer platinum complexes, and isomerism of Ni and Pt complexes.
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Hebert, Alexandra. "Mise au point de nouvelles techniques de radio-iodation et application au radiomarquage de molécules d'intérêt". Thesis, Normandie, 2019. http://www.theses.fr/2019NORMC413/document.
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Le radiomarquage de molécules d’intérêt avec des isotopes radioactifs est d'un grand intérêt pour la communauté scientifique, car il influe fortement sur le processus de découverte dans les sciences de la vie et en médecine nucléaire. Les molécules radiomarquées ont été largement utilisées pour évaluer les réactions biochimiques, pour mesurer la distribution in vivo d'une substance ou pour réaliser des tests RIA (RadioImmunoAssay). En médecine nucléaire, des radiopharmaceutiques pour la thérapie par ra-dio-isotopes (RIT) et des radiotraceurs pour des expériences d'imagerie telles que la TEP (tomographie par émission de positons), la tomographie par émission monophotonique (TEMP) ou la scintigraphie ont été décrites. Plusieurs isotopes de l'iode peuvent être utilisés à la fois pour le diagnostic et le traite-ment : 123I pour l'imagerie TEMP, 124I pour la TEP, 125I pour l'analyse biologique et 131I pour la radio-thérapie et la scintigraphie.Les méthodes classiques de radio-iodation reposent sur l'utilisation d'un précurseur pré-fonctionna-lisé, qui doit être synthétisé, isolé et purifié avant d'être introduit à l'étape de radio-iodation. La méthode par radioiododéstannylation est la méthode la plus populaire, bien que les précurseurs stannylés soient connus pour leur synthèse difficile et leur toxicité. Le développement de nouvelles méthodes de radio-iodation représente donc un grand intérêt dans le domaine de la radiochimie.Sur la base de travaux antérieurs, notre groupe a mis au point une méthode de radio-iodation de N-acylsulfonamides au moyen d’une radio-iodation C-H médiée par le palladium à température ambiante. Cette stratégie originale permet le radiomarquage de molécules d’intérêt dans des conditions très douces sans utiliser de précurseurs chimiques.Sur la base de la littérature, notre groupe développe actuellement une nouvelle méthode de radio-iodation de dérivés d’arylsilanes par radioiododésilylation dans des conditions douces. Cette méthodo-logie générale permet pour le moment le radiomarquage de dérivés d'arylsilanes activés en conditions doucesLabeling of (bio)molecules with radioactive isotopes is of high interest to for the scientific commu-nity, as it strongly impacts the discovery process in life science and nuclear medicine. Radiolabeled molecules have been extensively used to assess biochemical reactions, to measure in vivo distribution of a substance or to preform RIA (RadioImmunoAssay). In nuclear medicine, radio-therapeutics for RIT (RadioIsotope Therapy) and radio-tracers for molecular imaging experiments such as PET (Positron Emission Tomography), SPECT (Single Photon Emission Computed Tomography) or scintigraphy have been described. Several useful isotopes of iodine can be used for both diagnosis and therapy: 123I for SPECT imaging, 124I for PET imaging, 125I for biological assays and 131I for radio-therapy and scintig-raphy.Classical methods of radioiodination methods use a prefunctionalized precursor, which must be syn-thesized, isolated and purified before being introduced to the radio-iodination step. The radioiodode-stannylation method is the most popular method, although stannylated precursors are known for their difficult synthesis and their toxicity. The development of new methods of radioiodination is therefore of great interest in the field of radiochemistry.Based on a previous work, our group has developed a method to radio-iodinate N-acylsulfonamides through a room temperature palladium mediated C-H radio-iodination. This original strategy allows radiolabeling of biomolecules in very mild conditions without the use of chemical precursors.Based on literature, our group is now developping a new method to radio-iodinate arylsilyl derivates through radioiododesilylation in mild conditions. This general methodology allows for the moment the radiolabeling of activated arylsilyl derivates in mild conditions
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Barday, Manuel. "Rapid access to heterocycles using transition-metal catalysed C-H and C-C bond activation". Thesis, University of Liverpool, 2018. http://livrepository.liverpool.ac.uk/3029020/.
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Rogge, Torben. "Experimental and Computational Studies on Ruthenium- and Manganese-Catalyzed C-H and C-C Activation". Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2019. http://hdl.handle.net/21.11130/00-1735-0000-0005-1298-B.
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Holthausen, Michael H., Tayseer Mahdi, Christoph Schlepphorst, Lindsay J. Hounjet, Jan J. Weigand i Douglas W. Stephan. "Frustrated Lewis pair-mediated C–O or C–H bond activation of ethers". Royal Society of Chemistry, 2014. https://tud.qucosa.de/id/qucosa%3A35977.
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Protocols for the FLP-mediated transformation of ethers are presented. Distinct reaction pathways involving either C–O or C–H bond activation occur depending on the application of oxophilic B(C6F5)3 or hydridophilic tritylium ions as the Lewis acid.
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Duin, Marcel Adrianus. "Nucleophilic and electrophilic platinum compounds for C-H bond activation". [S.l. : Amsterdam : s.n.] ; Universiteit van Amsterdam [Host], 2004. http://dare.uva.nl/document/75218.
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Lopez, Suarez Laura. "Tetra-substituted olefin synthesis using palladium-catalysed C-H activation". Thesis, University of Edinburgh, 2012. http://hdl.handle.net/1842/5869.
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In an effort to obtain more efficient and greener chemical transformations, a substantial amount of research interest has been directed towards the use of arene C-H bonds as functional groups. Hydroarylation of alkynes through direct functionalisation of C-H bonds has been studied in recent years leading to the development of high-yielding metal-mediated processes. The main aim of the current work is the addition of a third component in the hydroarylation of alkynes trough C-H activation, in order to achieve a second C-C bond formation. Attempts at palladium-catalysed three-component reaction of unactivated indoles with alkynes and aryliodides are described. The three-component reaction was studied in the intermolecular mode with both aryliodides and the more reactive diaryliodonium salts. These latter regents are reactive arylating and oxidising agents and have been used in the direct arylation of indoles under mild conditions through a PdII-PdIV catalytic cycle. In both cases the three-component product was not obtained. The intramolecular version of the reaction using alkyne-tethered indoles and diaryliodonium salts is also described. In this case the tandem process was successful, especially when using ethynylbenzyl indole derivatives, the Z-tetrasubstituted olefins could be selectively obtained under mild conditions. Finally, a low-yielding synthesis of chromenes from propargylaryl ethers and diaryliodonium salts is also discussed.
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Liu, Xin-Zhu. "Development of late transition metal catalysed direct C-H activation". Thesis, Imperial College London, 2011. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.530451.
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Black, Stephen Ian. "Synthetic and mechanistic studies related to C-H bond activation". Thesis, Imperial College London, 1988. http://hdl.handle.net/10044/1/46966.
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Crosby, Sarah H. "Cyclometallated complexes of platinum : C-H activation, oxidation and reduction". Thesis, University of Warwick, 2011. http://wrap.warwick.ac.uk/55449/.
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Within this thesis, research related to the synthesis of Pt(II) and Pt(IV) cyclometallated complexes involving both aryl and alkyl C-H activation is discussed. The introduction reviews literature relevant to C-H activation, cyclometallation and reductive elimination, both historic and current. Four pyridine based pro-ligands, all with a 4-fluorophenyl substituent and a varying alkyl substituent, were synthesised in order to study both aryl and alkyl C-H activation. Initial reactions with K2PtCl4 led to the cyclometallation of the phenyl ring via a reversible aryl C-H activation, which then resulted in a variety of Pt(II) complexes by the addition of different co-ligands. Oxidation of these Pt(II) species gave Pt(IV) complexes, which subsequently underwent isomerisation to give the thermodynamic product. For the DMSO derivatives this was shown to occur via five coordinate complexes stabilised by agostic interactions with the alkyl chain and resulted in the first crystallographically characterised oxygen bound DMSO Pt(IV) complexes. Pt(II) and Pt(IV) sp2 cyclometallated complexes, each with an sp3 agostic interaction, were isolated and characterised when using the more sterically demanding tbutyl derivative of the pro-ligand. Subsequent alkyl C-H activation of the tbutyl group was observed via an intra-molecular transcyclometallation reaction to give complexes with an sp3 cyclometallation. From these species a series of complexes with a C(sp2)^N^C(sp3) tridentate ligand were also synthesised. It was also noted that a reversible rollover reaction of the Pt(II) agostic complex occurred in DMSO solvent by exchanging the C(sp2)^N cyclometallation for a C(sp2)^C(sp2) cyclometallation via decyclometallation, rotation about the central C-C bond and subsequent C-H activation. Reductive elimination of a chloride ligand with both sp2 and sp3 cyclometallated carbons occurred to give functionalised phenyl rings and tbutyl groups, respectively. Steric interactions were shown to play a major role in these reactions.
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Lackner, Sebastian. "Nickel-Catalyzed Secondary Alkylations and Fluoroalkylations via C–H Activation". Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2016. http://hdl.handle.net/11858/00-1735-0000-0028-87C8-1.
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Dupont, Jairton. "Activation-fonctionnalisation intramoleculaire de liaisons c-h par le palladium". Université Louis Pasteur (Strasbourg) (1971-2008), 1988. http://www.theses.fr/1988STR13197.
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Cooper, Stephen P. "The formation of polyheterocycles via palladium-catalysed C-H activation". Thesis, University of Bristol, 2015. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.682181.
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A new PdII-catalysed interrupted oxidative-Mizoroki-Heck reaction has been developed. This reaction enables the synthesis of a wide range of polyheterocycles in a single step starting with simple substrates and involves the addition of a tethered diene unit across two joined heterocycles. The reaction has proven to be general for dienes tethered to indoles and pyrroles (in blue) and for 1t-allylcapturing heterocycles such as furan, thiophene and pyrrole (in red). In some cases the non-oxidized variant can be obtained through careful choice of oxidant and reaction conditions The scope and mechanism of this reaction have been explored leading to the proposed mechanism shown below. C-H activation of the first, tethered, heterocycle (in this case pyrrole), leads to migratory insertion of the pendant alkene and rapid capture of the π-allyl system by the second heterocycle (in this case furan). Initial products show complete diastereoselectivity and in some cases can be isolated, or oxidized in situ to fully aromatic systems
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Dupont, Jairton. "Activation-fonctionnalisation intramoléculaire de liaisons C-H par le palladium". Grenoble 2 : ANRT, 1988. http://catalogue.bnf.fr/ark:/12148/cb376133600.
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Paine, Belinda Marie. "Ruthenium N-heterocyclic carbene complexes : C-H activation and catalysis". Thesis, University of Bath, 2005. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.425799.
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Zakrzewski, Jacek. "Design of flow processes for C-H activation-type reactions". Thesis, University of Cambridge, 2018. https://www.repository.cam.ac.uk/handle/1810/277176.
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The last 15 years have seen tremendous advances in using different metal catalysts to functionalize traditionally unreactive C–H bonds. Given the high potential of these seemingly ideal strategic bond forming reactions, the uptake of C–H activation in fine chemical manufacture is slow. Part of the reason for this deficiency is limited mechanistic understanding of these complex reactions. This can preclude industrial applications of either batch or continuous C–H activation processes. Owing to the synthetic utility of C–H activation reactions, it is highly desirable to design intensified processes for this family of transformations, what can possibly facilitate industrialisation of C–H activation reactions. Firstly, an ab initio process design of a novel C(sp3)–H activation reaction giving access to aziridines yielded a predictive mechanistic model that has been used in an in silico optimisation. The identified set of conditions was suitable for a scalable continuous process. A separation technique was developed, and the utility of the process was extended by a subsequent reaction, a nucleophilic ring opening. Secondly, a black-box optimisation of the investigated reaction was performed. The applied algorithm was able to identify a set of conditions fulfilling the set targets within few experimental trails. The second project has set out to design a process for a C–H oxidative carbonylation. A kinetic study has shown that the reaction is CO-starved even at elevated pressures and that there is an optimal CO concentration. The turn-over number was increased from 8 to nearly 500. Two scalable processes were then developed. The first was a batch process, characterised by a very low catalyst loading. The second was, to the best of author’s knowledge, the first continuous process for an oxidative carbonylation reaction. The continuous process was tested on several oxidative carbonylations yielding excellent results with virtually no optimisation performed. Finally, an environmental sustainability assessment was performed using both, simplified metrics and an LCI analysis. The developed mechanistic understanding allowed identification of sources of inherent inefficiencies of C–H activation reactions. Appropriate solutions to these obstacles were suggested. Thus, it is believed that a step towards generic principles of design of intensified, scalable processes for C–H activation-type reactions has been made.
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Loup, Joachim. "Selectivity Control in 3d Transition Metal-Catalyzed C–H Activation". Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2019. http://hdl.handle.net/21.11130/00-1735-0000-0003-C19E-1.
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