Ligand Design For Transition Metal Catalysis

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Ligand Design in Metal Chemistry

Author : Mark Stradiotto
Publisher : John Wiley & Sons
ISBN 13 : 1118839811
Total Pages : 448 pages
Book Rating : 4.1/5 (188 download)

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Book Synopsis Ligand Design in Metal Chemistry by : Mark Stradiotto

Download or read book Ligand Design in Metal Chemistry written by Mark Stradiotto and published by John Wiley & Sons. This book was released on 2016-09-01 with total page 448 pages. Available in PDF, EPUB and Kindle. Book excerpt: The design of ancillary ligands used to modify the structural and reactivity properties of metal complexes has evolved into a rapidly expanding sub-discipline in inorganic and organometallic chemistry. Ancillary ligand design has figured directly in the discovery of new bonding motifs and stoichiometric reactivity, as well as in the development of new catalytic protocols that have had widespread positive impact on chemical synthesis on benchtop and industrial scales. Ligand Design in Metal Chemistry presents a collection of cutting-edge contributions from leaders in the field of ligand design, encompassing a broad spectrum of ancillary ligand classes and reactivity applications. Topics covered include: Key concepts in ligand design Redox non-innocent ligands Ligands for selective alkene metathesis Ligands in cross-coupling Ligand design in polymerization Ligand design in modern lanthanide chemistry Cooperative metal-ligand reactivity P,N Ligands for enantioselective hydrogenation Spiro-cyclic ligands in asymmetric catalysis This book will be a valuable reference for academic researchers and industry practitioners working in the field of ligand design, as well as those who work in the many areas in which the impact of ancillary ligand design has proven significant, for example synthetic organic chemistry, catalysis, medicinal chemistry, polymer science and materials chemistry.

Ligand Design in Metal Chemistry

Author : Mark Stradiotto
Publisher : John Wiley & Sons
ISBN 13 : 1118839773
Total Pages : 448 pages
Book Rating : 4.1/5 (188 download)

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Book Synopsis Ligand Design in Metal Chemistry by : Mark Stradiotto

Rational Ligand Design for Potential Applications in Transition Metal Catalysis

Author : Sergey L. Sedinkin
Publisher :
ISBN 13 :
Total Pages : 144 pages
Book Rating : 4.:/5 (76 download)

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Book Synopsis Rational Ligand Design for Potential Applications in Transition Metal Catalysis by : Sergey L. Sedinkin

Download or read book Rational Ligand Design for Potential Applications in Transition Metal Catalysis written by Sergey L. Sedinkin and published by . This book was released on 2011 with total page 144 pages. Available in PDF, EPUB and Kindle. Book excerpt: Strategies to influence the steric and electronic properties of three classes of ligands were investigated. First, a compound class known as amino-dithiaphospholanes was studied. It is structurally related to phosphoramidites, which have been successfully applied in catalysis. The synthesis of amino-dithiaphospholanes was envisaged as an approach to electronically tuned phosphoramidites. General access to a variety of structurally modified amino-dithiaphospholanes from commercially available starting materials was developed. The electron donating properties of the new ligands were characterized by NMR. They were found to be more electron-donating than the corresponding phosphoramidites. The coordination chemistry of amino-dithiaphospholanes was investigated by synthesis of a series of iridium and rhodium complexes. Analysis of the physical data obtained for the complexes confirmed the increase in the electron density at the metal centers as a consequence of the increased basicity of the ligands. Second, a series of new, as well as known, phosphinooxazoline (PHOX) ligands was synthesized. A systematic study of structure-property relationships was performed with the PHOX ligands. It was shown that electronic tuning of the ligands is possible by varying the substituents on the phenyl ring. However, the tuning was seen to have unexpected, and often only minor influence on the electronic properties of the metal complexes. The efficiency of steric tuning was investigated by evaluation of X-ray structure analysis data of new iron PHOX complexes synthesized for the study. It was shown that the presence of substituents in the position a to the nitrogen atom of the oxazoline ring had the most profound impact on the geometries of the corresponding metal complexes. Finally, five new multidentate N, O donating ligands (L) were synthesized and characterized. Their coordination chemistry was investigated by preparation of new iron complexes mimicking naturally occurring non-heme enzymes. The general formulation [Fe(L)2](OTf)2, [Fe(L)(OTf)2] or [Fe(L)(OTf)](OTf) was established for the new complexes, and formation of only one isomer was confirmed for one of the complexes. The catalytic activity of the new compounds was demonstrated in the oxidation of activated methylene groups and alcohols to the corresponding ketones.

Ligand Design for Transition Metal Catalysis

Author : Séverine Duclos
Publisher :
ISBN 13 :
Total Pages : 134 pages
Book Rating : 4.:/5 (846 download)

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Book Synopsis Ligand Design for Transition Metal Catalysis by : Séverine Duclos

Download or read book Ligand Design for Transition Metal Catalysis written by Séverine Duclos and published by . This book was released on 2002 with total page 134 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Phosphorus(III)Ligands in Homogeneous Catalysis

Author : Paul C. J. Kamer
Publisher : John Wiley & Sons
ISBN 13 : 1118299701
Total Pages : 673 pages
Book Rating : 4.1/5 (182 download)

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Book Synopsis Phosphorus(III)Ligands in Homogeneous Catalysis by : Paul C. J. Kamer

Download or read book Phosphorus(III)Ligands in Homogeneous Catalysis written by Paul C. J. Kamer and published by John Wiley & Sons. This book was released on 2012-05-09 with total page 673 pages. Available in PDF, EPUB and Kindle. Book excerpt: Over the last 60 years the increasing knowledge of transition metal chemistry has resulted in an enormous advance of homogeneous catalysis as an essential tool in both academic and industrial fields. Remarkably, phosphorus(III) donor ligands have played an important role in several of the acknowledged catalytic reactions. The positive effects of phosphine ligands in transition metal homogeneous catalysis have contributed largely to the evolution of the field into an indispensable tool in organic synthesis and the industrial production of chemicals. This book aims to address the design and synthesis of a comprehensive compilation of P(III) ligands for homogeneous catalysis. It not only focuses on the well-known traditional ligands that have been explored by catalysis researchers, but also includes promising ligand types that have traditionally been ignored mainly because of their challenging synthesis. Topics covered include ligand effects in homogeneous catalysis and rational catalyst design, P-stereogenic ligands, calixarenes, supramolecular approaches, solid phase synthesis, biological approaches, and solubility and separation. Ligand families covered in this book include phosphine, diphosphine, phosphite, diphosphite, phosphoramidite, phosphonite, phosphinite, phosphole, phosphinine, phosphinidenene, phosphaalkenes, phosphaalkynes, P-chiral ligands, and cage ligands. Each ligand class is accompanied by detailed and reliable synthetic procedures. Often the rate limiting step in the application of ligands in catalysis is the synthesis of the ligands themselves, which can often be very challenging and time consuming. This book will provide helpful advice as to the accessibility of ligands as well as their synthesis, thereby allowing researchers to make a more informed choice. Phosphorus(III) Ligands in Homogeneous Catalysis: Design and Synthesis is an essential overview of this important class of catalysts for academic and industrial researchers working in catalyst development, organometallic and synthetic chemistry.

Ligand design for transition metal catalysis: From a-olefin polymerization to enantioselective reduction of prochiral alkenes

Author :
Publisher :
ISBN 13 :
Total Pages : pages
Book Rating : 4.:/5 (631 download)

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Book Synopsis Ligand design for transition metal catalysis: From a-olefin polymerization to enantioselective reduction of prochiral alkenes by :

Download or read book Ligand design for transition metal catalysis: From a-olefin polymerization to enantioselective reduction of prochiral alkenes written by and published by . This book was released on with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Le but cette thèse a été de concevoir des ligands organiques et d'étudier leurs propriétés de coordination et catalytiques avec des métaux de transition. Trois chapitres distincts sont présentés ici. Les propriétés de coordination du ligand [CpCo{(O)PR2}3]-, (noté LR-, R = OEt (LOEt- ) ou R = Et (LEt- )), vis-à-vis du zirconium (IV) ont été etudiées et comparées à celles de complexes analogues du cyclopentadienyl. L'addition d'un ou deux équivalents de LOEt- ou LEt- à [ZrCl4(THF)] ou [ZrCpCl] conduit aux complexes [Zr2(L'OEt)4] (1), [Zr(LOEt)2](OTos)2 ((3)(OTos)2), [Zr(LOEt)Cl3] (4) et [Zr(LEt)2]Cl2 ((5)Cl2) caractérisés cristallographiquement par diffraction de rayons X. Le complexe labile [Zr(LOEt)2Cl2] (2) subit une déalkylation d'Arbuzov pour donner le complexe dinucléaire 1. La synthèse et les propriétés de coordination de ligands compartimentés sont décrites. Les ligands macrocycliques H2LA (12) et H2LB (19) ont été conçus dans le but de mimer des analogues d'état de transition, pour la production d'anticorps catalytiques possédant de potentielles propriétés d'activation de liaisons C-H. La réaction du ligand 12 avec des cations vanadyl conduit à la formation du complexe dinucléaire [(VO)2(LA)]2+ (13) caractérisé par diffraction de rayons X. Les ligands amputés HLC (21) et H3LD (22) réagissent avec divers cations de métaux de transition pour donner des complexes, conçus afin d'être utilisés comme coenzymes pour les anticorps catalytiques. Le complexe du nickel [Ni2(LC)](CF3COO)3(MeOH) a également été caractérisé par diffraction de rayons X. Des pseudo-énantiomères de ligands phosphine-phosphinites POPo-An (2) et o-AnPOP (4)ont été synthétisés. Le complexe du platine [Pt(o-AnPOP)Cl2] (7) a été caractérisé par diffraction de rayons X. La contribution de l'asymétrie électronique a été quantifiée pour l'hydrogénation énantiosélective d'oléfines prochirales.

C-H Activation for Asymmetric Synthesis

Author : Françoise Colobert
Publisher : John Wiley & Sons
ISBN 13 : 3527343407
Total Pages : 294 pages
Book Rating : 4.5/5 (273 download)

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Book Synopsis C-H Activation for Asymmetric Synthesis by : Françoise Colobert

Download or read book C-H Activation for Asymmetric Synthesis written by Françoise Colobert and published by John Wiley & Sons. This book was released on 2019-11-11 with total page 294 pages. Available in PDF, EPUB and Kindle. Book excerpt: Provides, in one handbook, comprehensive coverage of one of the hottest topics in stereoselective chemistry Written by leading international authors in the field, this book introduces readers to C-H activation in asymmetric synthesis along with all of its facets. It presents stereoselective C-H functionalization with a broad coverage, from outer-sphere to inner-sphere C-H bond activation, and from the control of olefin geometry to the induction of point, planar and axial chirality. Moreover, methods wherein asymmetry is introduced either during the C-H activation or in a different elementary step are discussed. Presented in two parts?asymmetric activation of C(sp3)-H bonds and stereoselective synthesis implying activation of C(sp2)-H bonds?CH-Activation for Asymmetric Synthesis showcases the diversity of stereogenic elements, which can now be constructed by C-H activation methods. Chapters in Part 1 cover: C(sp3)-H bond insertion by metal carbenoids and nitrenoids; stereoselective C-C bond and C-N bond forming reactions through C(sp3)?H bond insertion of metal nitrenoids; enantioselective intra- and intermolecular couplings; and more. Part 2 looks at: C-H activation involved in stereodiscriminant step; planar chirality; diastereoselective formation of alkenes through C(sp2)?H bond activation; amongst other methods. -Covers one of the most rapidly developing fields in organic synthesis and catalysis -Clearly structured in two parts (activation of sp3- and activation of sp2-H bonds) -Edited by two leading experts in C-H activation in asymmetric synthesis CH-Activation for Asymmetric Synthesis will be of high interest to chemists in academia, as well as those in the pharmaceutical and agrochemical industry.

Ligand Platforms in Homogenous Catalytic Reactions with Metals

Author : Ryohei Yamaguchi
Publisher : John Wiley & Sons
ISBN 13 : 1118203518
Total Pages : 358 pages
Book Rating : 4.1/5 (182 download)

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Book Synopsis Ligand Platforms in Homogenous Catalytic Reactions with Metals by : Ryohei Yamaguchi

Download or read book Ligand Platforms in Homogenous Catalytic Reactions with Metals written by Ryohei Yamaguchi and published by John Wiley & Sons. This book was released on 2014-11-17 with total page 358 pages. Available in PDF, EPUB and Kindle. Book excerpt: Serving as a user's manual for synthetic organic and catalytic chemists, this book guides chemists in the design and choice of ligands to catalyze organic reactions and apply the results for more efficient, green, and practical synthesis. • Focuses on the role of ligands in metal complexes that catalyze green organic transformations: a hot topic in the area of organic synthesis and green chemistry • Offers a comprehensive resource to help readers design and choose ligands and understand selectivity/reactivity characteristics • Addresses a gap by taking novel ligand approaches and including up-to-date discussion on hydrogen transfers and reactions • Presents important industrial perspective and provides rational explanations of ligand effects, impacts, and novelty

Rational Design of Ligands for Transition Metal Catalysis

Author : Sima Yazdani
Publisher :
ISBN 13 :
Total Pages : 220 pages
Book Rating : 4.:/5 (13 download)

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Book Synopsis Rational Design of Ligands for Transition Metal Catalysis by : Sima Yazdani

Download or read book Rational Design of Ligands for Transition Metal Catalysis written by Sima Yazdani and published by . This book was released on 2021 with total page 220 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation includes exploring two scientific challenges, where both water oxidation catalysis and NH addition to alkynes will benefit greatly from the rational design of ligands. Chapter 1: The long-term goal for scientists is to use sunlight for the energy to split water. The main target of our research is the oxidation half reaction. Water oxidation catalysts have been reported by groups of Sun and Llobet but sustainable catalysis is still impaired by catalyst deactivation. This dissertation attempts to design robust catalysts through manipulating of the apical coordination sites. Chapter 2 uses phosphorus in the primary coordination sphere to create stronger axial ligand-ruthenium bonds; Chapter 3 uses a chelating macrocyclic ligand to reduce the chance of ligand loss. Chapter 4, focuses on the hydroamination of C-C multiple bonds as the most atom-efficient method for the introducing of nitrogen atoms into organic molecules.

Pincer Compounds

Author : David Morales-Morales
Publisher : Elsevier
ISBN 13 : 0128129328
Total Pages : 756 pages
Book Rating : 4.1/5 (281 download)

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Book Synopsis Pincer Compounds by : David Morales-Morales

Download or read book Pincer Compounds written by David Morales-Morales and published by Elsevier. This book was released on 2018-04-11 with total page 756 pages. Available in PDF, EPUB and Kindle. Book excerpt: Pincer Compounds: Chemistry and Applications offers valuable state-of-the-art coverage highlighting highly active areas of research—from mechanistic work to synthesis and characterization. The book focuses on small molecule activation chemistry (particularly H2 and hydrogenation), earth abundant metals (such as Fe), actinides, carbene-pincers, chiral catalysis, and alternative solvent usage. The book covers the current state of the field, featuring chapters from renowned contributors, covering four continents and ranging from still-active pioneers to new names emerging as creative strong contributors to this fascinating and promising area. Over a decade since the publication of Morales-Morales and Jensen’s The Chemistry of Pincer Compounds (Elsevier 2007), research in this unique area has flourished, finding a plethora of applications in almost every single branch of chemistry—from their traditional application as very robust and active catalysts all the way to potential biological and pharmaceutical applications. Describes the chemistry and applications of this important class of organometallic and coordination compounds Includes contributions from global leaders in the field, featuring pioneers in the area as well as emerging experts conducting exciting research on pincer complexes Highlights areas of promising and active research, including small molecule activation, earth abundant metals, and actinide chemistry

Metal-Ligand Co-operativity

Author : Gerard van Koten
Publisher : Springer Nature
ISBN 13 : 3030689166
Total Pages : 451 pages
Book Rating : 4.0/5 (36 download)

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Book Synopsis Metal-Ligand Co-operativity by : Gerard van Koten

Download or read book Metal-Ligand Co-operativity written by Gerard van Koten and published by Springer Nature. This book was released on 2021-03-29 with total page 451 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book provides researchers in the fields of organic chemistry, organometallic chemistry and homogeneous catalysis with an overview of significant recent developments in the area of metal-ligand cooperativity, with a focus on pincer architectures. The various contributions highlight the widespread impact of M–L co-operativity phenomena on modern organometallic chemistry and catalyst development. The development of efficient and selective catalytic transformations relies on the understanding and fine control of the various elementary reactions that constitutes a catalytic cycle. Co-operative ligands, which actively participate in bond making and bond breaking together to the metal they support, open up new avenues in this area. In particular, buttressing a weak or reactive metal-ligand bond by flanking coordinating arms in a pincer ligand design is proving a versatile strategy to access robust metal complexes that exhibit unusual and selective reactivity patterns.

Design and Synthesis of New Ligand Systems for Transition Metal Catalysed Carbon-carbon Cross-coupling, Hydrogenation and Hydrosilation

Download Design and Synthesis of New Ligand Systems for Transition Metal Catalysed Carbon-carbon Cross-coupling, Hydrogenation and Hydrosilation PDF Online Free

Author : Daniel Carleton
Publisher :
ISBN 13 :
Total Pages : 248 pages
Book Rating : 4.:/5 (857 download)

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Book Synopsis Design and Synthesis of New Ligand Systems for Transition Metal Catalysed Carbon-carbon Cross-coupling, Hydrogenation and Hydrosilation by : Daniel Carleton

Download or read book Design and Synthesis of New Ligand Systems for Transition Metal Catalysed Carbon-carbon Cross-coupling, Hydrogenation and Hydrosilation written by Daniel Carleton and published by . This book was released on 2013 with total page 248 pages. Available in PDF, EPUB and Kindle. Book excerpt: An ever increasing global requirement for consumables consequently increases the demand for often non-renewable resources, resulting in the need for greater efficiencies in synthetic processes. In order to achieve this goal, the field of organometallic catalysis has been ever growing to support the ideals of cleaner and greener chemistry. In this thesis studies concerning a series of new bidentate donor ligands employing both the NHC and PYA donor groups for use in transition metal catalysis is presented. The successful synthesis of the bidentate ligand N,N'-dimethyl-N''-pyridin-4-yl nicotinamide with both a remote NHC and PYA donor groups is reported, along with the synthesis of the precursor materials 1-methyl-3-(2-oxo-2-(pyridin-2-ylamino)ethyl)-1H-imidazol-3-ium and 1-methyl-3-(2-oxo-2-(pyridin-4-ylamino)ethyl)-1H-imidazol-3-ium for the formation of other bidentate ligands incorporating the imidazolium NHC and PYA donor groups. The iridium complex IrH(L-R4)(CO)(PPh3)2 containing the new ligand L-R4 was prepared through reaction of N,N'-dimethyl-N''-pyridin-4-yl nicotinamide with Vaskas Complex. Chapter one explains the ideology behind green chemistry and our constant drive to maintain a clean and green planet. Chapter two describes the effect of donor groups on a metal centre with focus on the NHC and PYA donor groups and their advantages over previous work in this area. Chapter three describes the development of synthetic routes to the new target ligands and chapter four explains the studies involving the metal precursor substrates and ligand coordination. Chapter five contains details of the relevant experimental data. The work described in this thesis will provide an excellent starting point for those wishing to further explore the synthesis and study of bidentate NHC and PYA donor ligands in catalysis by transition metals.

Homogeneous Transition-metal Catalysis

Author : Christopher Masters
Publisher : Springer
ISBN 13 :
Total Pages : 298 pages
Book Rating : 4.:/5 (43 download)

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Book Synopsis Homogeneous Transition-metal Catalysis by : Christopher Masters

Download or read book Homogeneous Transition-metal Catalysis written by Christopher Masters and published by Springer. This book was released on 1981 with total page 298 pages. Available in PDF, EPUB and Kindle. Book excerpt: Soluble catalysts are used extensively in many branches of chemistry and are indeed a vital constituent of many natural processes. They find wide application throughout the chemical industry where they assist in the production of several million tonnes of chemicals each year. Since homogeneous systems, especially those incorporating transition metals, often function effectively under milder conditions than their heterogeneous counterparts, they are becoming increasingly important at a time when the chemical industry in particular, and society in general, is seeking ways of conserving energy and of making the best possible use of available resources. My principal objective in· writing this book is to engender sufficient enthusiasm for, and knowledge of, the subject in the reader that he or she will be encouraged to begin, or continue, to make their own contribution to advancing our knowledge of homogeneous catalysis. After attempting to acquaint the reader with some of the ground rules I have tried to describe the .present scope, and the future potential, of this fascinating field of chemistry by drawing both on academic and on industrial data sources. This approach stems from a personal conviction that future progress could be considerably hastened by a more meaningful dialogue between chemists working both in industrial and in academic research institutions. Wherever possible, examples of the commercial application of homogeneous catalyst systems have been included and no attempt has been made in any way to disguise the many unresolved questions and exciting challenges which still pervade this rapidly developing area.

Asymmetric Organocatalysis Combined with Metal Catalysis

Author : Bruce A. Arndtsen
Publisher : Springer Nature
ISBN 13 : 3030438511
Total Pages : 211 pages
Book Rating : 4.0/5 (34 download)

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Book Synopsis Asymmetric Organocatalysis Combined with Metal Catalysis by : Bruce A. Arndtsen

Download or read book Asymmetric Organocatalysis Combined with Metal Catalysis written by Bruce A. Arndtsen and published by Springer Nature. This book was released on 2020-04-24 with total page 211 pages. Available in PDF, EPUB and Kindle. Book excerpt: The series Topics in Current Chemistry Collections presents critical reviews from the journal Topics in Current Chemistry organized in topical volumes. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience.Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field.The chapter "Enamine/Transition Metal Combined Catalysis: Catalytic Transformations Involving Organometallic Electrophilic Intermediates" is available open access under a CC BY 4.0 License via link.springer.com.

Modern Ylide Chemistry

Author : Viktoria H. Gessner
Publisher :
ISBN 13 : 9783319895468
Total Pages : 160 pages
Book Rating : 4.8/5 (954 download)

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Book Synopsis Modern Ylide Chemistry by : Viktoria H. Gessner

Download or read book Modern Ylide Chemistry written by Viktoria H. Gessner and published by . This book was released on 2018 with total page 160 pages. Available in PDF, EPUB and Kindle. Book excerpt: This volume covers recent advances in the chemistry of ylidic compounds with focus on their application in the design of ligands with unique donor properties, the development of novel organic transformations as well as the use of ylides in homogenous catalysis. Thereby, this volume particularly aims at the community of organic and organometallic chemists engaged in synthetic chemistry and catalysis as well as in the use of special ligands for the stabilization of unusual main group element species and the "transition-metal free" activation of element-element/hydrogen bonds. These fields of research are highly active and vivid research areas to which ylide chemistry has only recently started to contribute, but has already led to fascinating developments in most different directions. This volume highlights these recent developments, thus giving not only an overview over the past achievements, but also possibilities for future applications. To this end, the chapters selected in this volume combine different aspects of ylide chemistry, starting with theoretical aspects in ligand design followed by synthetic organic methods, catalytic transformations and complex chemistry.

Mechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods

Download Mechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods PDF Online Free

Author : Gui-Juan Cheng
Publisher : Springer
ISBN 13 : 9811045216
Total Pages : 140 pages
Book Rating : 4.8/5 (11 download)

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Book Synopsis Mechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods by : Gui-Juan Cheng

Download or read book Mechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods written by Gui-Juan Cheng and published by Springer. This book was released on 2017-06-07 with total page 140 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis presents detailed mechanistic studies on a series of important C-H activation reactions using combined computational methods and mass spectrometry experiments. It also provides guidance on the design and improvement of catalysts and ligands. The reactions investigated include: (i) a nitrile-containing template-assisted meta-selective C-H activation, (ii) Pd/mono-N-protected amino acid (MPAA) catalyzed meta-selective C-H activation, (iii) Pd/MPAA catalyzed asymmetric C-H activation reactions, and (iv) Cu-catalyzed sp3 C-H cross-dehydrogenative-coupling reaction. The book reports on a novel dimeric Pd-M (M = Pd or Ag) model for reaction (i), which successfully explains the meta-selectivity observed experimentally. For reaction (ii), with a combined DFT/MS method, the author successfully reveals the roles of MPAA ligands and a new C-H activation mechanism, which accounts for the improved reactivity and high meta-selectivity and opens new avenues for ligand design. She subsequently applies ion-mobility mass spectrometry to capture and separate the [Pd(MPAA)(substrate)] complex at different stages for the first time, providing support for the internal-base model for reaction (iii). Employing DFT studies, she then establishes a chirality relay model that can be widely applied to MPAA-assisted asymmetric C-H activation reactions. Lastly, for reaction (iv) the author conducts detailed computational studies on several plausible pathways for Cu/O2 and Cu/TBHP systems and finds a reliable method for calculating the single electron transfer (SET) process on the basis of benchmark studies.

Design of New Monodentate Ligands for Regioselectivity and Enantioselectivity Tuning in Late Transition Metal Catalysis

Author : Aaron A. Ruch
Publisher :
ISBN 13 :
Total Pages : 247 pages
Book Rating : 4.:/5 (126 download)

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Book Synopsis Design of New Monodentate Ligands for Regioselectivity and Enantioselectivity Tuning in Late Transition Metal Catalysis by : Aaron A. Ruch

Download or read book Design of New Monodentate Ligands for Regioselectivity and Enantioselectivity Tuning in Late Transition Metal Catalysis written by Aaron A. Ruch and published by . This book was released on 2016 with total page 247 pages. Available in PDF, EPUB and Kindle. Book excerpt: The ability of gold(I) to activate many types of unsaturated bonds toward nucleophilic attack was not widely recognized until the early 2000s. One major challenge in gold catalysis is the control over regioselectivity when there are two or more possible products as a result of complicated mechanistic pathways. It is well know that the choice of ligand can have dramatic effects on which pathway is being followed but very rarely are the reasons for this selectivity understood. The synthesis of new acyclic diaminocarbenes was developed and a study of the ligand effects on the regioselectivity of a gold-catalyzed domino enyne cyclization hydroarylation reaction and a Nazarov cyclization was undertaken. New chiral acyclic diaminocarbenes were also developed and tested along side new C3-symmetric phosphite ligands in an asymmetric intramolecular hydroamination of allenes. Structure activity correlations were developed for the potential use in further rational ligand design. The synthesis of 6a,7-dihydro-5-amino-dibenzo[c,g]chromene derivatives via a gold-catalyzed domino reaction of alkynylbenzaldehydes in the presence of secondary amines was developed. These were sent to be screened for biological activity.