Littérature scientifique sur le sujet « Transition-metal catalyzed organic transformations »

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Articles de revues sur le sujet "Transition-metal catalyzed organic transformations"

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Mhaske, Santosh, et Ranjeet Dhokale. « Transition-Metal-Catalyzed Reactions Involving Arynes ». Synthesis 50, no 01 (22 novembre 2017) : 1–16. http://dx.doi.org/10.1055/s-0036-1589517.

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The plethora of transformations attainable by the transition-metal-catalyzed reactions of arynes has found immense contemporary interest in the scientific community. This review highlights the scope and importance of transition-metal-catalyzed aryne reactions in the field of synthetic organic chemistry reported to date. It covers transformations achieved by the combination of arynes and various transition metals, which provide a facile access to a biaryl motif, fused polycyclic aromatic compounds, different novel carbocycles, various heterocycles, and complex natural products.1 Introduction2 Insertion of Arynes3 Annulation of Arynes4 Cycloaddition of Arynes5 Multicomponent Reactions of Arynes6 Miscellaneous Reactions of Arynes7 Total Synthesis of Natural Products Using Arynes8 Conclusion
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Kuninobu, Yoichiro. « Transition Metal-Catalyzed Highly Efficient and Novel Transformations ». Journal of Synthetic Organic Chemistry, Japan 71, no 5 (2013) : 425–32. http://dx.doi.org/10.5059/yukigoseikyokaishi.71.425.

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Takacs, J. M., S. C. Boito et Y. C. Myoung. « Recent Applications of Catalytic Metal-Mediated Carbocyclizations in Asymmetric Synthesis ». Current Organic Chemistry 2, no 3 (mai 1998) : 233–54. http://dx.doi.org/10.2174/1385272802666220128192732.

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Catalytic transition metal mediated transformations enable a variety of novel bond constructions and open up exciting new possibilities for synthesis. To date, a relatively limited number of these reactions have been used as key strategy elements in the asymmetric total synthesis of structurally complex natural products. This review examines several recent applications wherein the subset of transition-metal-catalyzed reactions, metal-catalyzed carbocyclizations, defines the key retrosynthetic transformation in the synthetic plan. The applications chosen and analyzed so as to highlight their efficiency, brevity and intrinsic elegance of design and are placed in context by comparison to complementary classical approaches to the target structure.
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Yuan, Jia, Ying Zhang, Hong Yu, Cuiying Wang, Sixuan Meng, Jian Chen, Guang-Ao Yu et Chi-Ming Che. « Transition metal complexes with functionalized indenyl phosphine ligands : structures and catalytic properties ». Organic & ; Biomolecular Chemistry 20, no 3 (2022) : 485–97. http://dx.doi.org/10.1039/d1ob01884a.

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This review summarizes the recent development of the use and impact of indenyl phosphines in the coordination chemistry and transition-metal-catalysed transformations, especially in E–H (E = H, C, Si and B) bonds activation, and palladium-catalyzed cross-coupling reactions.
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Zuo, Linhong, Teng Liu, Xiaowei Chang et Wusheng Guo. « An Update of Transition Metal-Catalyzed Decarboxylative Transformations of Cyclic Carbonates and Carbamates ». Molecules 24, no 21 (31 octobre 2019) : 3930. http://dx.doi.org/10.3390/molecules24213930.

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Functionalized cyclic organic carbonates and carbamates are frequently used in a number of transition metal-catalyzed decarboxylative reactions for the construction of interesting molecules. These decarboxylative transformations have attracted more and more research attention in recent years mainly due to their advantages of less waste generation and versatile reactivities. On the basis of previous reviews on this hot topic, the present review will focus on the development of transition metal-catalyzed decarboxylative transformations of functionalized cyclic carbonates and carbamates in the last two years.
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Sala, Roberto, Camilla Loro, Francesca Foschi et Gianluigi Broggini. « Transition Metal Catalyzed Azidation Reactions ». Catalysts 10, no 10 (12 octobre 2020) : 1173. http://dx.doi.org/10.3390/catal10101173.

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A wide range of methodologies for the preparation of organic azides has been reported in the literature for many decades, due to their interest as building blocks for different transformations and their applications in biology as well as in materials science. More recently, with the spread of the use of transition metal-catalyzed reactions, new perspectives have also materialized in azidation processes, especially concerning the azidation of C–H bonds and direct difunctionalization of multiple carbon-carbon bonds. In this review, special emphasis will be placed on reactions involving substrates bearing a leaving group, hydroazidation reactions and azidation reactions that proceed with the formation of more than one bond. Further reactions for the preparation of allyl and vinyl azides as well as for azidations involving the opening of a ring complete the classification of the material.
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Xu, Qing, Changqiu Zhao, Yongbo Zhou, Shuangfeng Yin et Libiao Han. « Transition Metal-Catalyzed Transformations of P(O)—H Bonds ». Chinese Journal of Organic Chemistry 32, no 10 (2012) : 1761. http://dx.doi.org/10.6023/cjoc201207024.

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Della Ca’, Nicola. « Palladium-Catalyzed Reactions ». Catalysts 11, no 5 (30 avril 2021) : 588. http://dx.doi.org/10.3390/catal11050588.

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Palladium is probably the most versatile and exploited transition metal in catalysis due to its capability to promote a myriad of organic transformations both at laboratory and industrial scales (alkylation, arylation, cyclization, hydrogenation, oxidation, isomerization, cross-coupling, cascade, radical reactions, etc [...]
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Landelle, Grégory, Armen Panossian, Sergiy Pazenok, Jean-Pierre Vors et Frédéric R. Leroux. « Recent advances in transition metal-catalyzed Csp2-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation ». Beilstein Journal of Organic Chemistry 9 (15 novembre 2013) : 2476–536. http://dx.doi.org/10.3762/bjoc.9.287.

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In the last few years, transition metal-mediated reactions have joined the toolbox of chemists working in the field of fluorination for Life-Science oriented research. The successful execution of transition metal-catalyzed carbon–fluorine bond formation has become a landmark achievement in fluorine chemistry. This rapidly growing research field has been the subject of some excellent reviews. Our approach focuses exclusively on transition metal-catalyzed reactions that allow the introduction of –CFH2, –CF2H, –C n F2 n +1 and –SCF3 groups onto sp² carbon atoms. Transformations are discussed according to the reaction-type and the metal employed. The review will not extend to conventional non-transition metal methods to these fluorinated groups.
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Marset, Xavier, et Gabriela Guillena. « Deep Eutectic Solvents as à-la-Carte Medium for Transition-Metal-Catalyzed Organic Processes ». Molecules 27, no 23 (2 décembre 2022) : 8445. http://dx.doi.org/10.3390/molecules27238445.

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Our society is facing a tremendous challenge to become more sustainable in every sphere of life. Regarding the chemical industry, one of the most significant issues to be addressed is the use of volatile organic compounds (VOCs) as solvents because they are petrol-derived and most of them are toxic and flammable. Among the possible solutions, deep eutectic solvents (DESs) have emerged as sustainable alternatives to VOCs in organic catalyzed transformations and other fields. The advantages of these new reaction media are not only related to their more benign physical and chemical properties and, for most of them, their renewable sources but also due to the possibility of being recycled after their use, increasing the sustainability of the catalyzed process in which they are involved. However, their use as media in catalytic transformations introduces new challenges regarding the compatibility and activity of known catalysts. Therefore, designed catalysts and “à-la-carte” DESs systems have been developed to overcome this problem, to maximize the reaction outcomes and to allow the recyclability of the catalyst/media system. Over the last decade, the popularity of these solvents has steadily increased, with several examples of efficient metal-catalyzed organic transformations, showing the efficiency of the catalysts/DES system, compared to the related transformations carried out in VOCs. Additionally, due to the inherent properties of the DES, unknown transformations can be carried out using the appropriated catalyst/DES system. All these examples of sustainable catalytic processes are compiled in this review.
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Thèses sur le sujet "Transition-metal catalyzed organic transformations"

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Das, Pralay. « New reactions and methodology : studies on transition metal catalyzed organic transformations ». Thesis, University of North Bengal, 2005. http://hdl.handle.net/123456789/775.

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Ganguly, Bhaskar. « Transition-metal catalyzed organic transformations and application towards the synthesis of heterocyclic compounds ». Thesis, University of North Bengal, 2017. http://ir.nbu.ac.in/handle/123456789/2650.

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Gandolfo, Eugenio. « Light-driven Metal-catalyzed Asymmetric Transformations ». Doctoral thesis, Universitat Rovira i Virgili, 2021. http://hdl.handle.net/10803/672439.

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Resum Una molècula en el seu estat excitat ofereix una reactivitat completament diferent de la del seu estat fonamental. Pot comportar-se tant com a millor oxidant com a millor reductor, permetent així noves transformacions a causa de la capacitat de generar radicals intermedis en condicions suaus. El principal objectiu científic d'aquesta tesi doctoral va ser investigar l'excitació directa de substrats i intermedis de reacció per desbloquejar noves vies de reacció, permetent transformacions asimètriques catalitzades per metalls les quals serien inviables sota el domini tèrmic. Amb aquesta finalitat, vaig investigar la química de les 4-alquil-1,4-dihidropiridines (4-alquil-DHP) com a font d'electrons i precursors de radicals tant en el seu estat excitat com en el seu estat fonamental. En el primer projecte, vaig aprofitar les propietats dels 4-alquil-DHP en el seu estat excitat, actuant com forts fotorreductors i font de radicals, per permetre l'acoblament creuat asimètric d'acil catalitzat amb níquel i així, accedir a cetones α, α- disubstituïdes altament enantioenriquides. En el segon projecte, vaig estudiar com, mitjançant l'excitació de la llum, era possible desviar la reactivitat establerta en l'estat fonamental d'un complex quiral d’organoiridi, permetent processos mecanístics originals inabastables en el domini tèrmic. En particular, vam provar un complex particular de η3-aliliridio (III) quiral per al qual estimem un potencial d'oxidació de ̴ +1.24 V en l'estat excitat. Aquesta nova funció catalítica adquirida després de l'excitació a través de la llum es va aprofitar per desenvolupar un acoblament enantioselectiu creuat alquil-alquil entre alcohols benzil al·lílics i radicals α-amino, derivats de 4-alquil-DHP que serveixen com a fonts de radicals en estat fonamental.
Resumen Una molécula en su estado excitado ofrece una reactividad completamente diferente a la de su estado fundamental. Puede comportarse tanto como mejor oxidante como mejor reductor, lo que permite nuevas transformaciones debido a la capacidad de generar radicales intermedios en condiciones suaves. El principal objetivo científico de esta tesis doctoral fue investigar la excitación directa de sustratos e intermedios de reacción para desbloquear nuevas formas de reacción, permitiendo transformaciones asimétricas catalizadas por metales las cuales serían inviables bajo el dominio térmico. Con este fin, investigué la química de las 4-alquil-1,4-dihidropiridinas (4-alquil-DHP) como fuente de electrones y precursores de radicales tanto en su estado excitado como en su estado fundamental. En el primer proyecto, aproveché las propiedades de los 4-alquil-DHP en su estado excitado, actuando como fuertes fotorreductores y fuente de radicales, para permitir el acoplamiento cruzado asimétrico de acilo catalizado con níquel y así, acceder a cetonas α, α-disustituidas altamente enantioenriquecidas. En el segundo proyecto, estudié cómo, mediante la excitación de la luz, era posible desviar la reactividad establecida en el estado fundamental de un complejo quiral de organoiridio, permitiendo procesos mecanísticos originales inalcanzables en el dominio térmico. En particular, probamos un complejo particular de η3-aliliridio (III) quiral para el cual estimamos un potencial de oxidación de ̴ +1.24 V en el estado excitado. Esta nueva función catalítica adquirida tras su excitación con la luz se aprovechó para desarrollar un acoplamiento cruzado enantioselectivo alquil-alquilo entre alcoholes bencil alílicos y radicales α-amino, derivados de 4-alquil-DHP que sirven como fuentes de radicales en estado fundamental.
Abstract An excited-state molecule offers a completely different reactivity than in its ground state. It can be both a better oxidant and a better reductant, thus enabling novel transformations due to the ability to generate radical intermediates under mild conditions. The main scientific objective of this doctoral thesis was to investigate the direct excitation of substrates and intermediates to unlock novel reactivity manifolds, enabling asymmetric metal-catalyzed transformations unfeasible under the thermal domain. To this end, I exploited the chemistry of 4-alkyl-1,4-dihydropyridines (4-alkyl-DHPs) in either their excited- and ground-state as sources of electrons and radical precursors. In the first project, I exploited the excited-state properties of 4-alkyl-DHPs, serving as strong photoreductant and radicals source, to enable an asymmetric nickel-catalyzed acyl cross-coupling to access highly enantioenriched α,α-disubstituted ketones. In the second project, I studied how, by means of light-excitation, it was possible to divert the established ground-state reactivity of an organoiridium chiral complex, enabling mechanistically original processes unattainable in the thermal domain. In particular, we probed a particular chiral η3-allyliridium(III) complex for which we estimated an oxidation potential of ̴ +1.24 V in the excited state. This novel catalytic function acquired upon light excitation was exploited to develop an enantioselective alkyl-alkyl cross-coupling between benzyl allylic alcohols and α-amino radicals, derived from 4-alkyl-DHPs serving as ground-state radical sources.
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Nimmagadda, Sri Krishna. « Asymmetric Transformations Catalyzed By Chiral BINOL Alkaline Earth Metal Phosphate Complexes ». Scholar Commons, 2016. http://scholarcommons.usf.edu/etd/6554.

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Small molecule hydrogen bond donors have emerged as versatile catalysts in asymmetric synthesis. Within this class, chiral BINOL phosphoric acid is regarded as one of the pioneer catalysts used in several asymmetric transformations. The ability of the catalyst to activate the substrates could be controlled in two different ways. (1) Dual activation/bifunctional activation of substrate by hydrogen bond interactions or ion pairing with phosphoric acid or (2) By forming chiral BINOL phosphate metal complex that could significantly alter the interactions in chiral space. In particular, chiral alkaline earth metal phosphate complexes have unique advantages as catalysts owing to the ubiquitous availability of alkaline earth metals, strong Brønsted basicity of their counterions, mild but significant Lewis acidity of the metal and their ability to coordinate at multiple reactive sites due to large ionic radius. Chapter 1 summarizes the recent development of alkaline earth metal complexes in asymmetric catalysis. My thesis dissertation is focused on the application of chiral alkaline earth metal phosphate complexes in novel asymmetric reactions. In Chapter 2, we disclosed an efficient asymmetric one-pot synthesis of chiral 1,3-oxazolidines and chiral 1,3-oxazinanes. Chiral oxazolidines and oxazinanes are widely used as auxiliaries in asymmetric transition metal catalysis and also key structural motifs in natural products with biological activities. We developed a new synthetic method for chiral 1,3-oxazolidines which follows the enantioselective addition of alcohols to imines catalyzed by chiral 3,3’-(triisopropylphenyl)-derived BINOL magnesium phosphate to form hemiaminal intermediate, which then undergoes mild base mediated intramolecular nucleophilic substitution to afford highly enantioselective 1,3-oxazolidines and 1,3-oxazinanes in good yields. In Chapter 3, we developed the first catalytic enantioselective desymmetrization process for the synthesis of novel axially chiral cyclohexylidene oxime ethers. Even though these molecules were found to be optically active in 1910, methods to synthesize these molecules are scarce. We have developed an efficient desymmetrization process of 4-phenyl cyclohexanones with phenoxyamines catalyzed by chiral BINOL strontium phosphate complex to afford highly enantioselective products. We then extended this methodology to the dynamic kinetic resolution of 2-substituted cyclohexanones to form chiral 2-substituted cyclohexyl oximes in good enantioselectivities, as demonstrated in Chapter 4. We further demonstrated the utility of these compounds by converting them to chiral 2-aryl cyclohexylamines which are important synthetic intermediates.
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Tan, Peng Wen. « Transition metal catalyzed reactions and functionalized group transformations ». Thesis, University of Oxford, 2017. https://ora.ox.ac.uk/objects/uuid:336947d0-c3c7-4c45-9849-d3231c53ab42.

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The overall objective of this thesis is to develop contemporary transition-metal-catalyzed strategies and applications to access various biologically and chemically relevant compounds in a direct and elegant fashion.
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Song, Xuejing. « Studies of transition metal catalyzed propylene polymerization ». Thesis, University of Oxford, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.308611.

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Zweni, Pumza P. « Dendrimer-transition metal catalyzed oxidation and reduction reactions ». Thesis, University of Ottawa (Canada), 2005. http://hdl.handle.net/10393/10529.

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This project was launched with the aim of developing dendrimer catalysts for oxidation and reduction reactions. Poly(amidoamine) (PAMAM) and poly(propyleneimine) (PPI) dendrimers were of interest because of their well-established synthesis. Chapter 1 describes the fundamentals of dendrimers and provides a brief insight of their application in catalysis. In particular, examples of dendritic catalysts that have been previously employed as oxidation and reduction catalysts are presented. Chapter 2 presents the synthesis and characterization of silica-supported PAMAM dendrimers, their phosphomethylation with Ph2 PCH2OH, and their complexation to palladium complexes. Chapter 3 reports the application of the silica-supported PAMAM-Pd complexes to the oxidation of alkenes to methyl ketones under Wacker-type conditions as well as the use of tBuOOH as the oxidant in these reactions. Chapter 4 discusses the use of the above-mentioned complexes to catalyze the selective hydrogenation of dienes to monoolefins in the presence of H2 under mild reaction conditions. Chapter 5 presents our efforts in modifying PPI dendrimers with the salen moiety to give ligands that are coordinated to the metals Ti and V. Attempts at using the former complexes to promote the epoxidation of alkenes and the latter complexes to catalyze the epoxidation of olefinic alcohols are discussed.
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Trono, Corazon. « Transition metal catalyzed synthesis of glycoclusters from sugar alkynes ». Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2001. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/MQ58515.pdf.

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Tatsumi, Kenta. « Transition Metal-Catalyzed Novel Transformations of Acid Chlorides and Acid Anhydrides ». Kyoto University, 2019. http://hdl.handle.net/2433/242519.

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Duvvuri, Krishnaja. « Transition Metal Catalyzed Enantioselective Hydroboration and Hydrovinylation of Alkenes ». The Ohio State University, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=osu1524049349604356.

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Livres sur le sujet "Transition-metal catalyzed organic transformations"

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Kazmaier, Uli, dir. Transition Metal Catalyzed Enantioselective Allylic Substitution in Organic Synthesis. Berlin, Heidelberg : Springer Berlin Heidelberg, 2012. http://dx.doi.org/10.1007/978-3-642-22749-3.

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Kazmaier, Uli. Transition Metal Catalyzed Enantioselective Allylic Substitution in Organic Synthesis. Berlin, Heidelberg : Springer-Verlag Berlin Heidelberg, 2012.

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Yamaguchi, Ryohei. Ligand platforms in homogenous catalytic reactions with metals : Practice and applications for green organic transformations. Hoboken, New Jersey : Wiley, 2015.

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Wang, Jianbo, Chi‐Ming Che et Michael P. Doyle, dir. Transition Metal‐Catalyzed Carbene Transformations. Wiley, 2022. http://dx.doi.org/10.1002/9783527829170.

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Wang, Jianbo. Transition Metal-Catalyzed Carbene Transformations. Wiley & Sons, Limited, John, 2022.

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Wang, Jianbo. Transition Metal-Catalyzed Carbene Transformations. Wiley & Sons, Incorporated, John, 2022.

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Wang, Jianbo. Transition Metal-Catalyzed Carbene Transformations. Wiley & Sons, Limited, John, 2021.

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Wang, Jianbo. Transition Metal-Catalyzed Carbene Transformations. Wiley & Sons, Incorporated, John, 2022.

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Wu, Xiao-Feng. Transition Metal-Catalyzed Indole Synthesis : Transition Metal-Catalyzed Heterocycle Synthesis Series. Elsevier Science & Technology Books, 2017.

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Toste, F. Dean, et A. Stephen K. Hashmi. Modern Gold Catalyzed Synthesis. Wiley-VCH Verlag GmbH, 2012.

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Chapitres de livres sur le sujet "Transition-metal catalyzed organic transformations"

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Guillena, Gabriela, et Diego J. Ramón. « Metal-Catalyzed Methodologies ». Dans Stereoselective Multiple Bond-Forming Transformations in Organic Synthesis, 307–38. Hoboken, NJ, USA : John Wiley & Sons, Inc, 2015. http://dx.doi.org/10.1002/9781119006220.ch11.

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Sandoval, Christian A., Ryoji Noyori, Qi-Lin Zhou, Andreas Pfaltz, Xue-Long Hou et Hisashi Yamamoto. « An Overview of Recent Developments in Metal-Catalyzed Asymmetric Transformations ». Dans Organic Chemistry - Breakthroughs and Perspectives, 335–66. Weinheim, Germany : Wiley-VCH Verlag GmbH & Co. KGaA, 2012. http://dx.doi.org/10.1002/9783527664801.ch9.

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Praneeth, V. K. K., et Thomas R. Ward. « Metal-Catalyzed Organic Transformations Inside a Protein Scaffold using Artificial Metalloenzymes ». Dans Coordination Chemistry in Protein Cages, 203–19. Hoboken, NJ, USA : John Wiley & Sons, Inc., 2013. http://dx.doi.org/10.1002/9781118571811.ch8.

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Shao, Lixiong, Jianmei Lu et Min Shi. « Transition Metal-Catalyzed Transformations of VDCPs ». Dans SpringerBriefs in Molecular Science, 41–45. Berlin, Heidelberg : Springer Berlin Heidelberg, 2012. http://dx.doi.org/10.1007/978-3-642-27573-9_3.

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Russo, Francesco, Luke R. Odell, Kristofer Olofsson, Peter Nilsson et Mats Larhed. « Microwave-Heated Transition Metal-Catalyzed Coupling Reactions ». Dans Microwaves in Organic Synthesis, 607–71. Weinheim, Germany : Wiley-VCH Verlag GmbH & Co. KGaA, 2013. http://dx.doi.org/10.1002/9783527651313.ch15.

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Grossman, Robert B. « Transition-Metal-Catalyzed and -Mediated Reactions ». Dans The Art of Writing Reasonable Organic Reaction Mechanisms, 256–309. New York, NY : Springer New York, 1999. http://dx.doi.org/10.1007/978-1-4757-3030-2_6.

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Grossman, Robert B. « Transition-Metal-Mediated and -Catalyzed Reactions ». Dans The Art of Writing Reasonable Organic Reaction Mechanisms, 341–414. Cham : Springer International Publishing, 2019. http://dx.doi.org/10.1007/978-3-030-28733-7_6.

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Grossman, Robert B. « Transition-Metal-Catalyzed and -Mediated Reactions ». Dans The Art of Writing Reasonable Organic Reaction Mechanisms, 270–333. New York, NY : Springer New York, 2003. http://dx.doi.org/10.1007/0-387-21545-x_6.

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Moberg, Christina. « Molybdenum-Catalyzed and Tungsten-Catalyzed Enantioselective Allylic Substitutions ». Dans Transition Metal Catalyzed Enantioselective Allylic Substitution in Organic Synthesis, 209–34. Berlin, Heidelberg : Springer Berlin Heidelberg, 2011. http://dx.doi.org/10.1007/3418_2011_11.

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Brandsma, L., H. D. Verkruijsse et S. F. Vasilevsky. « Copper-Catalyzed Aminoalkylation of Acetylenes ». Dans Application of Transition Metal Catalysts in Organic Synthesis, 61–67. Berlin, Heidelberg : Springer Berlin Heidelberg, 1999. http://dx.doi.org/10.1007/978-3-642-60328-0_4.

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Actes de conférences sur le sujet "Transition-metal catalyzed organic transformations"

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Huszár, Bianka, Zoltán Mucsi et György Keglevich. « Transition Metal-Catalyzed, “Ligand Free” P–C Coupling Reactions under MW Conditions ». Dans International Electronic Conference on Synthetic Organic Chemistry. Basel Switzerland : MDPI, 2022. http://dx.doi.org/10.3390/ecsoc-26-13647.

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Padwa, Albert. « Synthesis of Polycyclic Ring Systems Using Transition Metal Catalyzed Cyclizations of Diazo Alkynyl Ketones ». Dans The 4th International Electronic Conference on Synthetic Organic Chemistry. Basel, Switzerland : MDPI, 2000. http://dx.doi.org/10.3390/ecsoc-4-01782.

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Rapports d'organisations sur le sujet "Transition-metal catalyzed organic transformations"

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Transition metal catalyzed transformations of unsaturated molecules. Office of Scientific and Technical Information (OSTI), janvier 1989. http://dx.doi.org/10.2172/5417738.

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