Academic literature on the topic 'Intramolecular hydroamination'
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Journal articles on the topic "Intramolecular hydroamination"
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Tussing, Sebastian, Miriam Ohland, Garrit Wicker, Ulrich Flörke, and Jan Paradies. "Borane-catalyzed indole synthesis through intramolecular hydroamination." Dalton Transactions 46, no. 5 (2017): 1539–45. http://dx.doi.org/10.1039/c6dt04725d.
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Crimmin, Mark R., Ian J. Casely, and Michael S. Hill. "Calcium-Mediated Intramolecular Hydroamination Catalysis." Journal of the American Chemical Society 127, no. 7 (February 2005): 2042–43. http://dx.doi.org/10.1021/ja043576n.
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Roesky, P., S. Blechert, A. Zulys, M. Dochnahl, D. Hollmann, K. Löhnwitz, and J. S. Herrmann. "Intramolecular Hydroamination Route to Heterocycles." Synfacts 2006, no. 5 (May 2006): 0438. http://dx.doi.org/10.1055/s-2006-934360.
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Zhang, Wen, Jenny B. Werness, and Weiping Tang. "Intramolecular hydroamination of conjugated enynes." Tetrahedron 65, no. 16 (April 2009): 3090–95. http://dx.doi.org/10.1016/j.tet.2008.09.045.
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Feng, Zhijun, Yun Wei, Shuangliu Zhou, Guangchao Zhang, Xiancui Zhu, Liping Guo, Shaowu Wang, and Xiaolong Mu. "Reactivity of functionalized indoles with rare-earth metal amides. Synthesis, characterization and catalytic activity of rare-earth metal complexes incorporating indolyl ligands." Dalton Transactions 44, no. 47 (2015): 20502–13. http://dx.doi.org/10.1039/c5dt03214h.
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Foster, Daven, Pengchao Gao, Ziyun Zhang, Gellért Sipos, Alexandre N. Sobolev, Gareth Nealon, Laura Falivene, Luigi Cavallo, and Reto Dorta. "Design, scope and mechanism of highly active and selective chiral NHC–iridium catalysts for the intramolecular hydroamination of a variety of unactivated aminoalkenes." Chemical Science 12, no. 10 (2021): 3751–67. http://dx.doi.org/10.1039/d0sc05884j.
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Krieck, Sven, Diana Kalden, Ansgar Oberheide, Lydia Seyfarth, Hans-Dieter Arndt, Helmar Görls, and Matthias Westerhausen. "Synthesis and catalytic activity of tridentate N-(2-pyridylethyl)-substituted bulky amidinates of calcium and strontium." Dalton Transactions 48, no. 7 (2019): 2479–90. http://dx.doi.org/10.1039/c8dt04905j.
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Chen, Jun, Hong-Mei Guo, Quan-Qing Zhao, Jia-Rong Chen, and Wen-Jing Xiao. "Visible light-driven photocatalytic generation of sulfonamidyl radicals for alkene hydroamination of unsaturated sulfonamides." Chemical Communications 54, no. 50 (2018): 6780–83. http://dx.doi.org/10.1039/c7cc09871e.
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Otero, Antonio, Agustín Lara-Sánchez, José A. Castro-Osma, Isabel Márquez-Segovia, Carlos Alonso-Moreno, Juan Fernández-Baeza, Luis F. Sánchez-Barba, and Ana M. Rodríguez. "Synthesis and structural characterization of amido heteroscorpionate rare-earth metal complexes and hydroamination of aminoalkenes." New Journal of Chemistry 39, no. 10 (2015): 7672–81. http://dx.doi.org/10.1039/c5nj00930h.
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Peng, Xingao, Atsushi Kaga, Hajime Hirao, and Shunsuke Chiba. "Hydroamination of alkenyl N-arylhydrazones mediated by t-BuOK for the synthesis of nitrogen heterocycles." Organic Chemistry Frontiers 3, no. 5 (2016): 609–13. http://dx.doi.org/10.1039/c6qo00053c.
Full textDissertations / Theses on the topic "Intramolecular hydroamination"
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Rizk, Toni. "Synthesis of pyridines and pyrazines using intramolecular hydroamination." Thesis, University of Ottawa (Canada), 2010. http://hdl.handle.net/10393/28453.
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Despite recent progress, the scope and efficiency of intramolecular hydroamination has not yet reached its full synthetic potential. In particular, cyclizations to form 6-membered rings and applications in the synthesis of aromatic nitrogen heterocycles remain rare, despite the potential to access a variety of medicinally relevant heterocycles. The intramolecular hydroamination of alkynes presented offers a general approach to such nitrogen heterocycles from appropriately substituted acyclic precursors, in which the oxime functionality allows for a milder cyclization event and allows subsequently for the installation of one additional unsaturation (via loss of H2O). The discovery and optimization of an acid-catalyzed, hydroamination-isomerization-aromatization route for the synthesis of pyridines and pyrazines will be presented and discussed.*
*Please refer to dissertation for diagrams.
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Wixey, James S. "Novel calcium complexes applied to intramolecular hydroamination catalysis." Thesis, Cardiff University, 2012. http://orca.cf.ac.uk/37858/.
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This thesis discusses the synthesis, characterisation, and reactivity studies of a range of new chiral calcium complexes supported by various polydentate N-donor ligands and their suitability as catalysts for intramolecular hydroamination. Chapter One outlines the case for developing organocalcium complexes, including a general overview of their current application to a variety of heterofunctionalisation reactions. Chapter Two introduces the chiral ethylene diamines which are extensively used as calcium supporting ligands and later as precursors for the synthesis of bisimidazoline and potential imoxazoline ligands. Chapter Two provides details of the diamine synthesis and includes studies related to racemisation concerns of the chiral centre. Chapter Three discusses novel calcium complexes supported by the chiral ethylene diamine analogues presented in Chapter Two. Complex synthesis, characterisation, and catalytic performance in intramolecular hydroamination is probed and discussed. Chapter Four details a range of new bisimidazoline ligands and their employment as supporting ligands on calcium. The catalytic performance of the resulting complexes in intramolecular hydroamination is subsequently analysed and discussed. Chapter Five investigates the attempted development of a total synthetic pathway to a new class of imoxazoline ligand and related issues. Chapter Six contains all experimental procedures, characterising data pertaining to all new compounds and complexes presented in this Thesis. Appendices A-K contain additional catalytic figures and tables of crystallographic data for all new crystallographically characterised compounds. Summary sheets of every literature and new compound presented mentioned in this Thesis are also included, along with copies of both printed publications resulting from this Thesis at the time of submission.
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Arbour, Jannine Louise. "Metal-mediated intramolecular hydroamination and hydro(acy)alkoxylation reactions." Thesis, Imperial College London, 2012. http://hdl.handle.net/10044/1/9203.
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This PhD thesis describes work undertaken to effect asymmetric catalysis in hydroamination and hydro(acy)alkoxylation reactions of allenes. The introductory Chapter provides an overview of recent advances in asymmetric heterofunctionalisation reactions of allenes. This includes intra- and inter-molecular reactions involving C-N and C-O bond formations. Chapter 2 begins by comparing the preparation of a γ-allenic alcohol by two different synthetic routes and its subsequent use in intramolecular hydroalkoxylation reactions using copper(II) and silver(I) salts. From this study, the ability of silver diphosphine complexes to facilitate enantioselective hydroalkoxylation reactions in a 5-exo-trig fashion was discovered. Extensive reaction optimisation was undertaken, however only moderate ee’s and conversions were observed. In Chapter 3, the use of other metal Lewis acids to catalyse hydroalkoxylation reactions of γ-allenic alcohols is presented. DFT calculations undertaken by a colleague (Prof H. S. Rzepa) were used to rationalise the observed regioselectivities with silver(I), zinc(II), and tin(II) triflates. From DFT calculations, the metal counteranion was found to be intimately involved in the C-O bond formation. In the following two Chapters, the possibility of asymmetric synthesis by using chiral anionic ligands is discussed. In Chapter 4, additional γ-allenic alcohols and β-allenic acids were synthesised for intramolecular hydroalkoxylation or hydroacyalkoxylation reactions respectively. In Chapter 5, the respective γ-allenic amines were prepared for intramolecular hydroamination. In both cases, the outcome, scope and limitations of the reaction are discussed. In Chapter 6, an overall conclusion and future work is discussed. The last Chapter contains experimental procedures and characterisation data of all the compounds synthesised during the course of this project.
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Hunt, Ashley D. "Intramolecular Cope-type Hydroamination of Alkenes and Alkynes Using Hydrazides." Thèse, Université d'Ottawa / University of Ottawa, 2011. http://hdl.handle.net/10393/19881.
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Nitrogen-containing molecules are ubiquitous in both natural products and pharmaceutical drugs, thus an efficient method for the formation of these motifs is of great importance. Hydroamination, that is the addition of an N-H bond across an unsaturated carbon-carbon bond of an alkene or alkyne, stands out as a potential approach to obtain such molecules. To date, most research in this area relies on transition-metal catalysis to enable such reactivity. In efforts directed towards metal-free alternatives, we have developed a simple, metal-free hydroamination of alkenes using hydrazides. Further investigation into the corresponding reactivity of alkynes with hydrazides has provided access to novel azomethine imine products. In Chapter 2, expansion of the substrate scope with respect to the intramolecular hydroamination of alkenes using hydrazides, as well as studies directed towards elucidation of the mechanism of this reaction will be presented. The intramolecular hydroamination of alkynes using hydrazides and methods to access and isolate the azomethine imine products formed will be discussed in Chapter 3.
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Shasha, Adelle. "Metal-Catalysed Hydroamination." Science. School of Chemistry, 2007. http://hdl.handle.net/2123/1710.
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Doctor of Philosophy(PhD),This thesis describes the synthesis of terminal and internal amino and amidoalkynes and their hydroamination (cyclisation) catalysed by the complex (bis(N-methylimidazol-2-yl)methane)dicarbonylrhodium(I) tetraphenylborate (1). A series of analogous palladium complexes were also prepared and investigated for catalytic hydroamination. The scope of the rhodium(I) complex (1) for the intramolecular hydroamination of more complex amino and amidoalkyne substrates was investigated. This was made possible with the synthesis of aliphatic substrates, namely, 4 pentyn 1 amide (3) and 5 hexyn 1 amide (4) and a number of aromatic substrates, namely, 1, 4 diamino-2, 5 diethynylbenzene (5), 1, 4-diamino-2, 5 bis(phenylethynyl)benzene (6), 2, 3-diamino-1, 4-diethynylbenzene (7), 2, 3-diamino-1, 4-bis(phenylethynyl)benzene (8), 1, 5-bis(acetamido)-2, 4-diethynylbenzene (9), N-(acetyl)-2-ethynylbenzylamine (10) and N-(acetyl)-2-(phenylethynyl)benzylamine (11). The rhodium(I) complex (1) catalytically cyclised the aliphatic 4 pentyn 1 amide (3) regioselectively to the 6 membered ring, 3, 4 dihydro 2 pyridone (64) as the sole product. Attempts to cyclise 5 hexyn 1 amide (4) to produce either the 6 or 7 membered ring were unsuccessful. Compounds 5, 6, 7 and 8 were doubly cyclised to 1, 5 dihydro pyrrolo[2, 3 f]indole (71), 1, 5-dihydro-2, 6-diphenyl-pyrrolo[2, 3 f]indole (73), 1, 8-dihydro-pyrrolo[2, 3 g]indole (74) and 1, 8-dihydro-2, 7-diphenyl-pyrrolo[2, 3 g]indole (75) respectively. The aromatic amides with terminal acetylenes 9 and 10 cyclised to give 1, 7 diacetyl pyrrolo[3, 2 f]indole (76) and N (acetyl) 1, 2 dihydroisoquinoline (77) respectively. However, attempts to cyclise 11 were unsuccessful. Thus the rhodium(I) complex (1) successfully catalysed via hydroamination both terminal and internal acetylenic amine and amide substrates, to give pyridones, indoles and isoquinolines. Cationic and neutral palladium complexes incorporating the bidentate heterocyclic nitrogen donor ligand bis(N-methylimidazol-2-yl)methane (bim; 2) were synthesised: [Pd(bim)Cl2] (15), [Pd(bim)2][BF4]2 (17) [Pd(bim)(Cl)(CH3)] (14), [Pd(bim)(CH3)(NCCH3)][BF4] (16). All of the complexes were active as catalysts for the intramolecular hydroamination reaction, using the cyclisation of 4 pentyn 1 amine (21) to 2 methyl 1 pyrroline (22) as the model test reaction. Percentage conversions, turnover numbers and reaction profiles for each complex were compared to the rhodium(I) complex (1). These studies have shown that the catalytic activity was not significantly dependent on the bim donor ligand or the choice of metal. Substitution of the bim (2) ligand with the COD ligand and the use of methanol as the solvent did impact significantly on the efficiency of the hydroamination reactions.
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Shasha, Adelle. "Metal-Catalysed Hydroamination." Thesis, The University of Sydney, 2006. http://hdl.handle.net/2123/1710.
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This thesis describes the synthesis of terminal and internal amino and amidoalkynes and their hydroamination (cyclisation) catalysed by the complex (bis(N-methylimidazol-2-yl)methane)dicarbonylrhodium(I) tetraphenylborate (1). A series of analogous palladium complexes were also prepared and investigated for catalytic hydroamination. The scope of the rhodium(I) complex (1) for the intramolecular hydroamination of more complex amino and amidoalkyne substrates was investigated. This was made possible with the synthesis of aliphatic substrates, namely, 4 pentyn 1 amide (3) and 5 hexyn 1 amide (4) and a number of aromatic substrates, namely, 1, 4 diamino-2, 5 diethynylbenzene (5), 1, 4-diamino-2, 5 bis(phenylethynyl)benzene (6), 2, 3-diamino-1, 4-diethynylbenzene (7), 2, 3-diamino-1, 4-bis(phenylethynyl)benzene (8), 1, 5-bis(acetamido)-2, 4-diethynylbenzene (9), N-(acetyl)-2-ethynylbenzylamine (10) and N-(acetyl)-2-(phenylethynyl)benzylamine (11). The rhodium(I) complex (1) catalytically cyclised the aliphatic 4 pentyn 1 amide (3) regioselectively to the 6 membered ring, 3, 4 dihydro 2 pyridone (64) as the sole product. Attempts to cyclise 5 hexyn 1 amide (4) to produce either the 6 or 7 membered ring were unsuccessful. Compounds 5, 6, 7 and 8 were doubly cyclised to 1, 5 dihydro pyrrolo[2, 3 f]indole (71), 1, 5-dihydro-2, 6-diphenyl-pyrrolo[2, 3 f]indole (73), 1, 8-dihydro-pyrrolo[2, 3 g]indole (74) and 1, 8-dihydro-2, 7-diphenyl-pyrrolo[2, 3 g]indole (75) respectively. The aromatic amides with terminal acetylenes 9 and 10 cyclised to give 1, 7 diacetyl pyrrolo[3, 2 f]indole (76) and N (acetyl) 1, 2 dihydroisoquinoline (77) respectively. However, attempts to cyclise 11 were unsuccessful. Thus the rhodium(I) complex (1) successfully catalysed via hydroamination both terminal and internal acetylenic amine and amide substrates, to give pyridones, indoles and isoquinolines. Cationic and neutral palladium complexes incorporating the bidentate heterocyclic nitrogen donor ligand bis(N-methylimidazol-2-yl)methane (bim; 2) were synthesised: [Pd(bim)Cl2] (15), [Pd(bim)2][BF4]2 (17) [Pd(bim)(Cl)(CH3)] (14), [Pd(bim)(CH3)(NCCH3)][BF4] (16). All of the complexes were active as catalysts for the intramolecular hydroamination reaction, using the cyclisation of 4 pentyn 1 amine (21) to 2 methyl 1 pyrroline (22) as the model test reaction. Percentage conversions, turnover numbers and reaction profiles for each complex were compared to the rhodium(I) complex (1). These studies have shown that the catalytic activity was not significantly dependent on the bim donor ligand or the choice of metal. Substitution of the bim (2) ligand with the COD ligand and the use of methanol as the solvent did impact significantly on the efficiency of the hydroamination reactions.
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Higginbotham, Mari C. M. "Gold(I)-catalysed synthesis of cyclic sulfamidates by intramolecular allene hydroamination." Thesis, Heriot-Watt University, 2014. http://hdl.handle.net/10399/2789.
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The work reported in this thesis outlines the gold(I)-catalysed synthesis of cyclic sulfamidates by intramolecular allene hydroamination. Work carried out in an attempt to prepare a novel acyl anion equivalent is also included but endeavours were halted after one year of study. The thesis is divided into six chapters: Chapter one provides an introduction to the reactivity of gold, current metal-catalysed hydroamination reactions and allene structure, synthesis and reactivity. The current synthetic methods for the preparation of sulfamidates and their uses is also covered. Chapter two outlines the attempted use of the Burgess reagent to prepare olefinically substituted sulfamidates and the attempts to reverse regioselectivity in sulfamidate synthesis. Chapter three includes an initial proof of concept in gold(I) catalysis and an account of substrate synthesis. Allenes were synthesised by Crabbé homologation or Johnson- Claisen rearrangement reactions. The allenes were then converted to the corresponding sulfamates. Chapter four outlines our studies of gold(I)-catalysed hydroamination. This includes optimisation of catalyst and the effects of substitution on reaction rate and stereochemical hypothesis. The current scope and limitations of this chemistry is also discussed. Chapter five outlines the research work attempted within the first year of study. The work focussed on the attempted preparation of a thermally unmasked acyl anion equivalent. Chapter six provides a formal report of the experimental procedures. Stereochemical abstract: All compounds with stereogenic centres were prepared as racemic mixtures but only one enantiomer is represented in the schemes.
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Arrowsmith, Merle. "Intramolecular hydroamination of aminoalkenes with group 2 precatalysts : mechanistic insights and ligand design." Thesis, University of Bath, 2011. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.538274.
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Long relegated to the background by the pre-eminence of magnesium-based, stoichiometric Grignard reagents, a distinct chemistry of the heavier alkaline earth metals, calcium, strontium and barium, is only now starting to emerge. As similarities have been drawn between the large, electropositive, redox-inert and d0 alkaline earth Ae2+ dications and the Ln3+ cations of the lanthanide series, a growing group 2-mediated catalytic chemistry has developed over the last decade, including polymerisation reactions, heterofunctionalisation reactions of multiple bonds and some rare examples of dehydrocoupling reactions. Among these catalytic reactions the magnesium- and calcium-catalysed intramolecular hydroamination of aminoalkenes has attracted particular interest. Mechanistic studies have demonstrated many parallels with the lanthanide-mediated catalytic cycle based upon successive σ-bond metathesis and insertion steps. In the first part of this thesis, further investigations into the hydroamination/cyclisation reaction have demonstrated the prominent role of the charge density of the catalytic group 2 cation (M = Mg, Ca, Sr, Ba), the beneficial influence of stabilising spectator ligands, and the importance of the choice of the reactive co-ligand for efficient catalyst initiation. Kinetic analyses of reactions monitored by NMR spectroscopy have given new insight into activation energies, entropic effects, substrate and product inhibition, and kinetic isotope effects, leading to a review of the previously suggested lanthanide-mimetic mechanism. In a second part, this study seeks to address two of the main challenges posed by the intramolecular hydroamination reaction in particular, and heavier alkaline earth-catalysed reactions in general: (i) The need to design new monoanionic spectator ligands capable of stabilising heteroleptic heavier alkaline earth complexes and preventing deleterious Schlenk-type ligand redistribution processes in solution; (ii) The stabilisation of highly reactive heteroleptic group 2 alkyl functionalities for fast, irreversible catalyst initiation and novel reactivity.
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Brinkmann, Christine. "Heavier group 2 metals : application to intermolecular hydroamination, C-F activation and intramolecular hydroalkoxylation." Thesis, Imperial College London, 2011. http://hdl.handle.net/10044/1/9155.
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This thesis describes the reactivity of different heavier alkaline earth catalysts [M{X(SiMe3)2}2(THF)n]m (M = Ca, Sr, Ba; X = N, CH; n= 0, 2; m= 1, 2) in the intermolecular hydroamination of styrene derivatives. The scope of these reactions with respect to the substrate was determined and detailed kinetic studies to establish rate law and temperature dependence of the hydroamination reactions reported were conducted. Overall, it was found that [Ca{N(SiMe3)2}2]2 is favoured enthalpically (Ca: ΔH‡ = 51 kJ∙mol-1, Sr: ΔH‡ = 71 kJ∙mol-1) however the corresponding strontium bis(amide) proved a significantly better catalyst, likely due to a favourably high entropy of activation value (Ca: ΔS‡ = -168 J/mol-1 ·K-1, Sr: ΔS‡ = -92 J∙mol-1∙K-1). Large kinetic isotope effects of 4.1 and 7.9 at 55 °C for the intermolecular hydroamination of styrene with piperidine mediated by [Ca{N(SiMe3)2}2]2 and [Sr{N(SiMe3)2}2]2, respectively, suggest a rate-determining alkene insertion into the M-N bond with immediate or concerted protonolysis. The methodology used in these hydroamination reactions was extended to simple dienes, diphenylacetylene and an activated enyne. The catalyst initiation of the metal bis(amides) with piperidine was shown to be reversible and the equilibrium constant solvent dependent. Novel calcium and strontium dialkyl complexes [M{CH(SiMe3)2}2(THF)2] (M= Ca, Sr) were used to overcome the problem of catalyst initiation and showed a different solvent dependence. An enhanced reactivity was found for the dialkyl complexes compared to the metal bis(amides). This increased reactivity allowed the application in new reactions such as the C-F activation of fluorobenzenes. Furthermore, the use of these catalytic systems was successfully extended to intramolecular hydroalkoxylation reactions of alkynyl alcohols in the formation of five- and six-membered enol ethers. In this case, [Ba{N(SiMe3)2}2]2 displayed significant reactivity although the “catalyst of choice” for these reactions proved to be strongly dependent on substrate substitution pattern. Through detailed kinetic studies the catalyst, substrate and temperature dependence of the cyclisation reaction were established and an unusual rate law with inverse substrate dependence proposed.
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Bennett, Stacey Danielle. "Novel Group 3/Lanthanide complexes and their application to intramolecular hydroamination and ring-opening polymerisation." Thesis, Cardiff University, 2013. http://orca.cf.ac.uk/58616/.
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This thesis describes the synthesis, characterisation and reactivity studies of a range of Group 3/Lanthanide complexes supported by bis(oxazolinyl)phenyl amide (BOPA). Chapter 1: Provides an introduction to the properties of the Lanthanides. Their application in asymmetric catalysis is reviewed, including catalysts supported by oxazoline ligands. Chapter 2 Describes density functional theory on a series of Group 3 BOPA complexes, the synthesis and characterisation of a new scandium amide-chloride precursor, thirty Group 3/lanthanide compounds supported by BOPA, six cation compounds supported by BOPA and three lithium BOPA compounds along with a discussion of the reactivity of compounds. Chapter 3: Describes the application of compounds described in Chapter 2 to the intermolecular hydroamination reaction of aminoolefins. Chapter 4: Describes a brief introduction to ring-opening polymerisation of rac-lactide and the application of compounds described in Chapter 2 to the ring-opening polymerisation of rac-lactide. Chapter 5: A brief introduction to luminescence is provided and the photophysical properties of a selection of diamagnetic complexes and all paramagnetic complexes discussed in Chapters 2 are described. Also, the synthesis, characterisation and photophysical properties of five Group 3/lanthanide compounds supported by pseudosubstrate ligands are described. Chapter 6: Details full experimental procedures and contains characterising data for all new compounds. Appendices A-B: Full tables of crystallographic data for all new crystallographically characterised compounds described herein are provided in Appendix A. Publications from this thesis are provided in Appendix B.
Book chapters on the topic "Intramolecular hydroamination"
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Beccalli, Egle M., Gianluigi Broggini, Michael S. Christodoulou, and Sabrina Giofrè. "Transition Metal-Catalyzed Intramolecular Amination and Hydroamination Reactions of Allenes." In Advances in Organometallic Chemistry, 1–71. Elsevier, 2018. http://dx.doi.org/10.1016/bs.adomc.2018.02.003.
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"C-N Ring-forming Reactions by Transition Metal-catalyzed Intramolecular Alkene Hydroamination." In Organic Synthesis, 30–31. Hoboken, NJ, USA: John Wiley & Sons, Inc., 2006. http://dx.doi.org/10.1002/0470056312.ch16.
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Chemler, S. R., and J. J. Kennedy-Ellis. "1.3 Copper-Catalyzed Alkene Difunctionalization." In Base-Metal Catalysis 1. Stuttgart: Georg Thieme Verlag KG, 2023. http://dx.doi.org/10.1055/sos-sd-238-00052.
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AbstractAlkene difunctionalization is a classic molecular transformation in organic synthesis, enabling the production of more-complex molecules from simple hydrocarbon-derived feedstocks. Alkene difunctionalizations catalyzed by copper complexes offer potentially more-sustainable protocols compared to those catalyzed by more-precious or -toxic metals. This chapter summarizes important recent advancements in the field, especially in the area of asymmetric catalysis. A number of copper-catalyzed intramolecular and intermolecular alkene difunctionalizations for the synthesis of cyclic and acyclic chiral amines and ethers, and related compounds, are presented. The reactions include alkene and/or diene hydroamination, hydroetherification, carboamination, carboetherification, diamination, oxyamination, and dicarbofunctionalization. Many of the reaction mechanisms involve a radical component either in the first or second bond-forming event. The ability of copper to engage with radicals in bond-forming events, including enantioselective ones, is a valuable aspect of many of these reactions.
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Taber, Douglass F. "Alkaloid Synthesis: (–)-α-Kainic Acid (Cohen), Hyacinthacine A2 (Fox), (–)-Agelastatin A (Hamada), (+)-Luciduline (Barbe), (+)-Lunarine (Fan), (–)-Runanine (Herzon)." In Organic Synthesis. Oxford University Press, 2015. http://dx.doi.org/10.1093/oso/9780190200794.003.0058.
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The intramolecular ene cyclization is still little used in organic synthesis. Theodore Cohen of the University of Pittsburgh trapped (J. Org. Chem. 2011, 76, 7912) the cyclization product from 1 with iodine to give 2, setting the stage for an enantiospecific total synthesis of (–)-α-kainic acid 3. Intramolecular alkene hydroamination has been effected with transition metal catalysts. Joseph M. Fox of the University of Delaware isomerized (Chem. Sci. 2011, 2, 2162) 4 to the trans cyclooctene 5 with high diastereocontrol. Deprotection of the amine led to spontaneous cyclization, again with high diastereocontrol to hyacinthacine A2 6. Yasumasa Hamada of Chiba University devised (Org. Lett. 2011, 13, 5744) a catalyst system for the enantioselective aziridination of cyclopentenone 7. The product 8 was carried on to the tricyclic alkaloid (–)-agelastatin A 9. Guillaume Barbe, now at Novartis in Cambridge, MA, effected (J. Org. Chem. 2011, 76, 5354) the enantioselective Diels-Alder cycloaddition of acrolein 11 to the dihydropyridine 10. Ring-opening ring-closing metathesis later formed one of the carbocyclic rings of (+)-luciduline 13, and set the stage for an intramolecular aldol condensation to form the other. Chun-An Fan of Lanzhou University employed (Angew. Chem. Int. Ed. 2011, 50, 8161) a Cinchona-derived catalyst for the enantioselective Michael addition to prepare 14. Although 14 and 15 were only prepared in 77% ee, crystallization to remove the racemic component of a later intermediate led to (+)-lunarine 16 in high ee. Seth B. Herzon of Yale University used (Angew. Chem. Int. Ed. 2011, 50, 8863) the enantioselective Diels-Alder addition with 18 to block one face of the quinone 17. Reduction of 19 followed by methylation delivered an iminium salt, only one face of which was open for the addition of an aryl acetylide. Thermolysis to remove the cyclopentadiene gave an intermediate that was carried on to (+)-runanine 20.
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Lambert, Tristan H. "New Methods for C–N Ring Construction." In Organic Synthesis. Oxford University Press, 2015. http://dx.doi.org/10.1093/oso/9780190200794.003.0055.
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The reduction of pyridines offers an attractive approach to piperidine synthesis, and now Toshimichi Ohmura and Michinori Suginome of Kyoto University have developed (J. Am. Chem. Soc. 2012, 134, 3699) a rhodium-catalyzed hydroboration of pyridines, including the reaction of 1 to produce 3. Timothy J. Donohoe at the University of Oxford has found (Org. Lett. 2011, 13, 2074) that pyridinium silanes 4 undergo intramolecular hydride transfer by treatment with TBAF to produce dihydropyridones (e.g., 5) with good diastereoselectivity. Enantioselective amination of allylic alcohols has proven challenging, but Ross A. Widenhoefer at Duke University has reported (Angew. Chem. Int. Ed. 2012, 51, 1405) that a chiral gold catalyst can effect such intramolecular cyclizations with good enantioselectivity, as in the synthesis of 7 from 6. Alternatively, Masato Kitamura at Nagoya University has developed (Org. Lett. 2012, 14, 608) a ruthenium catalyst that operates at as low as 0.05 mol% loading for the conversion of substrates such as 8 to 9. Efforts to replace transition metal catalysts with alkaline earth metal-based alternatives have been gaining increasing attention, and Kai C. Hultzsch at Rutgers University has found (Angew. Chem. Int. Ed. 2012, 51, 394) that the magnesium complex 12 is capable of catalyzing intramolecular hydroamination (e.g., 10 to 11) with high enantioselectivity. Meanwhile, a stereoselective Wacker-type oxidation of tert-butanesulfinamides such as 13 to produce pyrrolidine derivatives 14 has been disclosed (Org. Lett. 2012, 14, 1242) by Shannon S. Stahl at the University of Wisconsin at Madison. Though highly desirable, Heck reactions have rarely proven feasible with alkyl halides due to competitive β-hydride elimination of the alkyl palladium intermediates. Sherry R. Chemler at the State University of New York at Buffalo has demonstrated (J. Am. Chem. Soc. 2012, 134, 2020) a copper-catalyzed enantioselective amination Heck-type cascade (e.g., 15 and 16 to 17) that is thought to proceed via radical intermediates. David L. Van Vranken at the University of California at Irvine has reported (Org. Lett. 2012, 14, 3233) the carbenylative amination of N-tosylhydrazones, which proceeds through η3-allyl Pd intermediates constructed via carbene insertion. This chemistry was applied to the two-step synthesis of caulophyllumine B from vinyl iodide 18 and N-tosylhydrazone 19.
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Horino, Yoshikazu, Young Kwan Kim, and Tom Livinghouse. "New Classes of Highly Active Non-Metallocene Group 3 Catalysts for Intramolecular Alkene Hydroamination, Pinacolborane Hydroboration and Hydrosilylation." In 19th International Congress on Heterocyclic Chemistry, 64. Elsevier, 2003. http://dx.doi.org/10.1016/b978-0-08-044304-1.50057-5.
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Taber, Douglass. "New Methods for C-N Ring Construction." In Organic Synthesis. Oxford University Press, 2011. http://dx.doi.org/10.1093/oso/9780199764549.003.0055.
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Chaozhong Li of the Shanghai Institute of Organic Chemistry demonstrated (Organic Lett. 2008, 10, 4037) facile and selective Cu-catalyzed β-lactam formation, converting 1 to 2. Paul Helquist of the University of Notre Dame devised (Organic Lett. 2008, 10, 3903) an effective catalyst for intramolecular alkyne hydroamination, converting 3 into the imine 4. Six-membered ring construction worked well also. Jon T. Njardarson of Cornell University found (Organic Lett. 2008, 10, 5023) a Cu catalyst for the rearrangement of alkenyl aziridines such as 5 to the pyrroline 6. Philippe Karoyan of the UPMC, Paris developed (J. Org. Chem. 2008, 73, 6706) an interesting chiral auxiliary directed cascade process, converting the simple precursor 7 into the complex pyrrolidine 9. Sherry R. Chemler of the State University of New York, Buffalo devised (J. Am. Chem. Soc. 2008, 130, 17638) a chiral Cu catalyst for the cyclization of 10, to give 12 with substantial enantiocontrol. Wei Wang of the University of New Mexico demonstrated (Chem. Commun. 2008, 5636) the organocatalyzed condensation of 13 and 14 to give 16 with high enantio- and diastereocontrol. Two complementary routes to azepines/azepinones have appeared. F. Dean Toste of the University of California, Berkeley showed (J. Am. Chem. Soc. 2008, 130, 9244) that a gold complex catalyzed the condensation of 17 and 18 to give 19. Frederick G. West of the University of Alberta found (Organic Lett. 2008, 10, 3985) that lactams such as 20 could be ring-expanded by the addition of the propiolate anion 21. Takeo Kawabata of Kyoto University extended (Organic Lett . 2008, 10, 3883) “memory of chirality” studies to the cyclization of 23, demonstrating that 24 was formed in high ee. Paul V. Murphy of University College Dublin took advantage (Organic Lett . 2008, 10, 3777) of the well-known intramolecular addition of azides to alkenes, showing that the intermediate could be intercepted with nucleophiles such as thiophenol, to give the cyclized product 26 with high diastereocontrol.
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Hussein Mekni, Nejib Ben, and Noureddine Raouafi. "Coordination, Degrading Agent, Catalyst Property and Spectroscopy of Organocalcium Compounds." In The Synthetic Methods, Structures, and Properties of the Ca-Cσ Bond Organocalcium Containing Compounds, 56–82. BENTHAM SCIENCE PUBLISHERS, 2022. http://dx.doi.org/10.2174/9789815040647122010006.
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In addition to the coordination of the calcium to the n electron pairs, some examples of coordination to the π electron pairs are observed resulting from calcium interactions with highly conjugated systems. The complex structures vary from ordinary to close to the unexpected organocalcium inverse sandwich. The organocalcium Ca-C bond containing compounds are highly reactive. They degrade and act as degrading agents on the solvent. The study of the effect of five factors: temperature, concentration, organic group, counter ion and coordinated donor solvent, shows an intramolecular degradation mechanism. Organocalcium complexes are more stable in the THP than in the THF ethereal media. Calcium and organocalcium Ca-Cσ-bond containing derivatives are described as efficient pre-catalysts for catalytic conversions of alkenes by polymerization, hydroamination, hydrosilylation, hydrogenation, and hydrophosphination. The activation process is suggested as an electrostatic interaction between the alkene and Lewis acidic calcium metallic species, leading to both vertical and horizontal polarization of the π bond electron density, resulting in an incentive for nucleophilic attack. Some researchers illustrate that the organocalcium derivatives may be described as “Trojan horses” X-ray constitutes the most efficient technique to characterize the organocalcium structures for crystalized compounds, affording interesting information about angle values and bond lengths. The 43Ca, 13C and 1H NMR spectroscopy constitutes an alternative, secondary and complementary tool for characterizing both soluble, and even insoluble compounds, monitoring the reaction progress and making specific experimental manipulations. The coupling constants 1 JCa-C, and 2 JCa-C-H are not mentioned and there is no mass spectrometry nor IR spectroscopy studies
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Ye, Z. S. "40.1.8 Product Subclass 8: Piperazines." In Knowledge Updates 2021/2. Stuttgart: Georg Thieme Verlag KG, 2021. http://dx.doi.org/10.1055/sos-sd-140-00314.
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AbstractThe piperazine unit is widely distributed in natural products and life-saving small-molecule pharmaceuticals. It is the third most common nitrogen heterocycle occurring in pharmaceuticals approved by the U. S. Food and Drug Administration. This chapter covers strategies for the synthesis and transformations of piperazines, with both classical methods and recent developments reviewed. A major focus is on cyclization reactions such as intramolecular hydroaminations, multicomponent approaches, and routes from ethane-1,2-diamine substrates. Also discussed are approaches based on hydrogenation of (hydro)pyrazines by heterogeneous catalysis and by (asymmetric) homogeneous catalysis. Finally, a variety of transformations involving modification of a substituent on a piperazine ring are surveyed, including arylations, alkylations, and oxidations.