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Author: Laura Keiko Gilah Ackerman Publisher: ISBN: Category : Languages : en Pages : 186
Book Description
"This thesis describes the use of multiple transition metal catalysts for the selective formation of carbon-carbon bonds. While the majority of cross coupling reactions rely on one transition-metal catalyst which reacts with a stoichiometric metal reagent, the combination of two metal catalysts in reactions has the potential to significantly increase the expediency towards synthetic targets, eliminating the need for stoichiometric metal reagents and improving functional group compatibility. There are many precedents for the combination of catalysts in organic methodology, however relatively few examples of multimetallic catalyzed reactions exist, and even fewer examples exist where the mechanism between the two catalytic metals is understood. The aim of the projects communicated in this thesis is two-fold: (1) To design new and efficient ways to form useful carbon-carbon bonds (Csp2-Csp3, Csp2-Csp2, and Csp2-Csp2) from readily available starting materials and (2) to provide insight into how two transition metal catalysts can cooperate in a reaction to achieve high selectivity and yield. Chapter 1 reviews the importance of carbon-carbon bond formation and introduces the main methods of cross coupling, including the concept of multimetallic catalysis. Previous examples of dual metal catalysis are summarized in the literature and the advantages and challenges of using two metals in a catalytic system are discussed. Chapter 2 presents a nickel and cobalt catalyzed strategy for the formation of Csp2-Csp3 bonds. The first attempted cross electrophile couplings to form diarylmethanes from benzyl halides and aryl iodides is reported in moderate selectivity, followed by the strategic optimization of the co-catalytic system which enables higher yields and selectivity through the coupling of benzyl sulfonate esters with aryl halides. In this reaction, nickel reacts selectively with aryl halides through an oxidative addition step, while cobalt phthalocyanine generates radicals through an Sn2 reaction with benzyl sulfonate esters, followed by homolysis. The extension of this method to coupling benzyl phosphonate esters and primary and secondary benzyl chlorides is also presented. Chapter 3 reports the quest for and ultimate discovery of a multimetallic catalyzed Csp2-Csp2 coupling. Beginning with stoichiometric transmetalation studies for the coupling of aryl C-H bonds with aryl C-X bonds, the reaction of various metal aryl complexes based on iridium, ruthenium, copper, nickel, and palladium are described. While these reactions were ineffective in generating unsymmetrical biaryls, the catalytic combination of a nickel and palladium catalyst to couple aryl bromides with aryl trifluoromethanesulfonate esters for the design of a cross Ullman reaction was a success. This reaction provided access to a variety of unsymmetrical biaryls maintaining an equimolar catalyst loading of the two metals, and showed promise for later development of the formation of useful unsymmetrical bipyridines and dienes. The scope of this remarkable reaction, the origin of selectivity, and the enhancement in rate and selectivity by a KF additive is presented. Additionally, the optimization strategy towards coupling chlorobenzene and electron-rich aryl chlorides is communicated. Finally, this chapter includes the first attempted multimetallic catalyzed multicomponent reactions with the nickel and palladium as well as nickel and cobalt catalyzed systems, including carbonylation, and the difunctionalization of olefins and alkynes."--Pages xii-xiii.
Author: Laura Keiko Gilah Ackerman Publisher: ISBN: Category : Languages : en Pages : 186
Book Description
"This thesis describes the use of multiple transition metal catalysts for the selective formation of carbon-carbon bonds. While the majority of cross coupling reactions rely on one transition-metal catalyst which reacts with a stoichiometric metal reagent, the combination of two metal catalysts in reactions has the potential to significantly increase the expediency towards synthetic targets, eliminating the need for stoichiometric metal reagents and improving functional group compatibility. There are many precedents for the combination of catalysts in organic methodology, however relatively few examples of multimetallic catalyzed reactions exist, and even fewer examples exist where the mechanism between the two catalytic metals is understood. The aim of the projects communicated in this thesis is two-fold: (1) To design new and efficient ways to form useful carbon-carbon bonds (Csp2-Csp3, Csp2-Csp2, and Csp2-Csp2) from readily available starting materials and (2) to provide insight into how two transition metal catalysts can cooperate in a reaction to achieve high selectivity and yield. Chapter 1 reviews the importance of carbon-carbon bond formation and introduces the main methods of cross coupling, including the concept of multimetallic catalysis. Previous examples of dual metal catalysis are summarized in the literature and the advantages and challenges of using two metals in a catalytic system are discussed. Chapter 2 presents a nickel and cobalt catalyzed strategy for the formation of Csp2-Csp3 bonds. The first attempted cross electrophile couplings to form diarylmethanes from benzyl halides and aryl iodides is reported in moderate selectivity, followed by the strategic optimization of the co-catalytic system which enables higher yields and selectivity through the coupling of benzyl sulfonate esters with aryl halides. In this reaction, nickel reacts selectively with aryl halides through an oxidative addition step, while cobalt phthalocyanine generates radicals through an Sn2 reaction with benzyl sulfonate esters, followed by homolysis. The extension of this method to coupling benzyl phosphonate esters and primary and secondary benzyl chlorides is also presented. Chapter 3 reports the quest for and ultimate discovery of a multimetallic catalyzed Csp2-Csp2 coupling. Beginning with stoichiometric transmetalation studies for the coupling of aryl C-H bonds with aryl C-X bonds, the reaction of various metal aryl complexes based on iridium, ruthenium, copper, nickel, and palladium are described. While these reactions were ineffective in generating unsymmetrical biaryls, the catalytic combination of a nickel and palladium catalyst to couple aryl bromides with aryl trifluoromethanesulfonate esters for the design of a cross Ullman reaction was a success. This reaction provided access to a variety of unsymmetrical biaryls maintaining an equimolar catalyst loading of the two metals, and showed promise for later development of the formation of useful unsymmetrical bipyridines and dienes. The scope of this remarkable reaction, the origin of selectivity, and the enhancement in rate and selectivity by a KF additive is presented. Additionally, the optimization strategy towards coupling chlorobenzene and electron-rich aryl chlorides is communicated. Finally, this chapter includes the first attempted multimetallic catalyzed multicomponent reactions with the nickel and palladium as well as nickel and cobalt catalyzed systems, including carbonylation, and the difunctionalization of olefins and alkynes."--Pages xii-xiii.
Author: Stephen David Ramgren Publisher: ISBN: Category : Languages : en Pages : 511
Book Description
This dissertation describes the study of metal-catalyzed cross-coupling reactions to construct carbon-carbon and carbon-heteroatom bonds. The key feature of much of this work is the use of inexpensive Ni and Fe catalysts to enable the coupling of unconventional electrophilic substrates, specifically aryl O-sulfamates and O-carbamates. The ability to use O-sulfamates and O-carbamates in catalytic processes is notable, as these substrates are readily derived from phenols and can be used for directed arene functionalization. Chapter one provides a summary of the efforts towards using alcohol-based solvents for the Suzuki-Miyaura cross-coupling reaction. Emphasis is placed on the cross-coupling of heterocycles, which are commonly encountered in natural product synthesis and in the pharmaceutical sector. Chapters two, three, and four describe carbon-nitrogen bond forming reactions. Chapter two pertains to the nickel-catalyzed amination of sulfamates, which culminated in the synthesis of the antibacterial drug, linezolid. Chapter three covers the amination of aryl O-carbamates and their use in sequential functionalization/site-selective cross-couplings. Chapter four describes a more user-friendly variant of the amination reaction, which relies on a bench-stable Ni(II) precatalyst, rather than a more commonly used Ni(0) precatalyst. Chapters five, six, and seven focus on carbon-carbon bond formation via Fe-, Ni- and Pd-mediated processes. Chapter five pertains to iron-catalyzed couplings of sulfamates and carbamates to generate sp2-sp3 carbon-carbon bonds. This method can be used to assemble sterically-congested frameworks. Chapter six describes the nickel-catalyzed Suzuki-Miyaura reactions of halides and phenol derivatives in `green' solvents, which was applied to the preparative scale assembly of bis(heterocycles) using low nickel catalyst loadings. Chapter seven pertains to the acetylation of arenes using palladium catalysis, which provides a simple and efficient means for the construction of a variety of aryl methyl ketones.
Author: Rui Shang Publisher: Springer ISBN: 9811031932 Category : Science Languages : en Pages : 225
Book Description
This thesis presents the latest developments in new catalytic C–C bond formation methods using easily accessible carboxylate salts through catalytic decarboxylation with good atom economy, and employing the sustainable element iron as the catalyst to directly activate C–H bonds with high step efficiency. In this regard, it explores a mechanistic understanding of the newly discovered decarboxylative couplings and the catalytic reactivity of the iron catalyst with the help of density functional theory calculation. The thesis is divided into two parts, the first of which focuses on the development of a series of previously unexplored, inexpensive carboxylate salts as useful building blocks for the formation of various C–C bonds to access valuable chemicals. In turn, the second part is devoted to several new C–C bond formation methodologies using the most ubiquitous transition metal, iron, as a catalyst, and using the ubiquitous C–H bond as the coupling partner.
Author: Stanley M. Roberts Publisher: John Wiley & Sons ISBN: 0470862009 Category : Science Languages : en Pages : 268
Book Description
The chemist has a vast range of high-tech catalysts to use when working in fine chemical synthesis but the catalysts are generally hard to use and require both time, skill and experience to handle properly. The Catalysts for Fine Chemical Synthesis series contains tested and validated procedures which provide a unique range resources for chemists who work in organic chemistry. "... of great value to synthetic organic chemists..." (The Chemists, Summer 2003) Volume 3 in the series focuses on catalysts for carbon-carbon bond formation and presents practical and detailed protocols on how to use sophisticated catalysts by the "inventors" and "developers" who created them. The combination of protocols and review commentaries helps the reader to easily and quickly understand and use the new high-tech catalysts.
Author: Stanley M. Roberts Publisher: Wiley ISBN: 9780470861998 Category : Science Languages : en Pages : 0
Book Description
The chemist has a vast range of high-tech catalysts to use when working in fine chemical synthesis but the catalysts are generally hard to use and require both time, skill and experience to handle properly. The Catalysts for Fine Chemical Synthesis series contains tested and validated procedures which provide a unique range resources for chemists who work in organic chemistry. "... of great value to synthetic organic chemists..." (The Chemists, Summer 2003) Volume 3 in the series focuses on catalysts for carbon-carbon bond formation and presents practical and detailed protocols on how to use sophisticated catalysts by the "inventors" and "developers" who created them. The combination of protocols and review commentaries helps the reader to easily and quickly understand and use the new high-tech catalysts.
Author: Andrei K. Yudin Publisher: John Wiley & Sons ISBN: 3527633405 Category : Science Languages : en Pages : 541
Book Description
Written by an experienced editor widely acclaimed within the scientific community, this book covers everything fromo9xygen to nitrogen functionalities. From the contents: Palladium-Catalyzed Syntheses of Five-Member Saturated Heterocyclic and of Aromatic Heterodynes Palladium-Catalysis for Oxidative 1, 2-Difunctionalization of Alkenes Rhodium-Catalyzed Amination of C-H-Bonds Carbon-Heteroatom Bond Formation by RH(I)-Catalyzed Ring-Opening Reactions Transition Metal-Catalyzed Synthesis of Lactones and of Monocyclic and Fused Five-Membered Aromatic heterocycles the Formation of Carbon-Sulfur and Carbon-Selenium bonds by Substitution and Addition reactions catalyzed by Transition Metal Complexes New Reactions of Copper Acetylides Gold Catalyzed Addition of Nitrogen, Sulfur and Oxygen Nucleophiles to C-C Multiple Bonds. The result is an indispensable source of information for the Strategic Planning of the Synthetic routes for organic, catalytic and medicinal chemists, as well as chemists in industry.
Author: Timothy Patrick Montgomery Publisher: ISBN: Category : Languages : en Pages : 1092
Book Description
A central tenant of organic synthesis is the construction of carbon-carbon bonds. One of the traditional methods for carrying out such transformations is that of carbonyl addition. Unfortunately, traditional carbonyl addition chemistry suffers various drawbacks: preactivation, moisture sensitivity, and the generation of stoichiometric organometallic waste. The research presented in this dissertation focuses on the development of methods that make use of nucleophile-electrophile pairs generated in situ via transfer hydrogenation, which allow the formation of carbonyl or imine addition products from the alcohol or amine oxidation level; streamlining the construction of complex molecules from simple, readily available starting materials. Additionally, studies toward the total synthesis of the fibrinogen receptor inhibitor tetrafibricin, utilizing the methods developed in catalytic carbon-carbon bond formation through the addition, transfer or removal of hydrogen, are presented.
Author: Pradp Bgle Publisher: ISBN: 9785891842199 Category : Technology & Engineering Languages : en Pages : 0
Book Description
This book is a comprehensive guidebook that covers the recent advances in gold and silver co-operative catalysis for carbon-carbon and carbon-heteroatom bond formation. The use of gold and silver in catalysis has revolutionized the field of organic synthesis, allowing for the development of new reactions and strategies that were previously inaccessible. The Book provides an in-depth discussion of the various gold and silver co-operative catalysis strategies and their application in the synthesis of a wide range of organic molecules, including pharmaceuticals, natural products, and materials. The author describes the key steps involved in these reactions, including the design of suitable catalysts, optimization of reaction conditions, and purification of the products. Also covers the use of gold and silver co-operative catalysis in the synthesis of other important compounds such as heterocycles, carbenes, and vinylidene complexes. The author discusses the advantages and limitations of gold and silver co-operative catalysis compared to other catalytic systems and provides practical guidance for researchers interested in using these catalysts in their own synthetic projects. Overall, "Gold and Silver Co-Operative Catalysis for Carbon Bond Formation" is an essential reference for synthetic chemists, medicinal chemists, and material scientists who are interested in the development of new catalytic systems for carbon-carbon and carbon-heteroatom bond formation using gold and silver co-operative catalysis.
Author: Laura Keiko Gilah Ackerman
Author: Laura Keiko Gilah Ackerman
Author: Stephen David Ramgren
Author: Rui Shang
Author: Stanley M. Roberts
Author: Stanley M. Roberts
Author: Andrei K. Yudin
Author: Karen V. Baker
Author: Timothy Patrick Montgomery
Author: Pradp Bgle
Author: Michael J Krische