Download or read book Exploring the Chemistry of Intermediates in the Nickel Catalyzed Cross coupling of Alkyl Electrophiles written by Gavin David Jones and published by . This book was released on 2007 with total page 224 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Nickel Catalysis in Organic Synthesis written by Sensuke Ogoshi and published by John Wiley & Sons. This book was released on 2020-03-09 with total page 348 pages. Available in PDF, EPUB and Kindle. Book excerpt: A comprehensive reference to nickel chemistry for every scientist working with organometallic catalysts Written by one of the world?s leading reseachers in the field, Nickel Catalysis in Organic Synthesis presents a comprehensive review of the high potential of modern nickel catalysis and its application in synthesis. Structured in a clear and assessible manner, the book offers a collection of various reaction types, such as cross-coupling reactions, reactions for the activation of unreactive bonds, carbon dioxide fixation, and many more. Nickel has been recognized as one of the most interesting transition metals for homogeneous catalysis. This book offers an overview to the recently developed new ligands, new reaction conditions, and new apparatus to control the reactivity of nickel catalysts, allowing scientists to apply nickel catalysts to a variety of bond-forming reactions. A must-read for anyone working with organometallic compounds and their application in organic synthesis, this important guide: -Reviews the numerous applications of nickel catalysis in synthesis -Explores the use of nickel as a relatively cheap and earth-abundant metal -Examines the versatility of nickel catalysis in reactions like cross-coupling reactions and CH activations -Offers a resource for academics and industry professionals Written for catalytic chemists, organic chemists, inorganic chemists, structural chemists, and chemists in industry, Nickel Catalysis in Organic Synthesis provides a much-needed overview of the most recent developments in modern nickel catalysis and its application in synthesis.
Download or read book Ni and Fe Based Cross Coupling Reactions written by Arkaitz Correa and published by Springer. This book was released on 2016-11-26 with total page 342 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.
Download or read book Cross Coupling Reactions written by Norio Miyaura and published by Springer. This book was released on 2003-07-01 with total page 253 pages. Available in PDF, EPUB and Kindle. Book excerpt: In 1972, a very powerful catalytic cycle for carbon-carbon bond formation was 2 first discovered by the coupling reaction of Grignard reagents at the sp -carbon. Over the past 30 years, the protocol has been substantially improved and expanded to other coupling reactions of Li,B,N,O,Al,Si,P,S,Cu,Mn,Zn,In,Sn, and Hg compounds. These reactions provided an indispensable and simple methodology for preparative organic chemists. Due to the simplicity and rel- bility in the carbon-carbon, carbon-heteroatom, and carbon-metalloid bo- formations,as well as high efficiency of the catalytic process,the reactions have been widely employed by organic chemists in various fields. Application of the protocol ranges from various syntheses of complex natural products to the preparation of biologically relevant molecules including drugs, and of sup- molecules, and to functional materials. The reactions on solid surfaces allow robot synthesis and combinatorial synthesis. Now, many organic chemists do not hesitate to use transition metal complexes for the transformation of org- ic molecules. Indeed, innumerable organic syntheses have been realized by the catalyzed reactions of transition metal complexes that are not achievable by t- ditional synthetic methods. Among these, the metal-catalyzed cross-coupling reactions have undoubtedly contributed greatly to the development of such a new area of “metal-catalyzed organic syntheses”. An excellent monograph for the cross-coupling reactions and other met- catalyzed C-C bond-forming reactions recently appeared in Metal-catalyzed Cross-coupling Reactions (Wiley-VCH,1998).
Download or read book Nickel Catalysis in Organic Synthesis written by Sensuke Ogoshi and published by John Wiley & Sons. This book was released on 2019-11-26 with total page 386 pages. Available in PDF, EPUB and Kindle. Book excerpt: A comprehensive reference to nickel chemistry for every scientist working with organometallic catalysts Written by one of the world?s leading reseachers in the field, Nickel Catalysis in Organic Synthesis presents a comprehensive review of the high potential of modern nickel catalysis and its application in synthesis. Structured in a clear and assessible manner, the book offers a collection of various reaction types, such as cross-coupling reactions, reactions for the activation of unreactive bonds, carbon dioxide fixation, and many more. Nickel has been recognized as one of the most interesting transition metals for homogeneous catalysis. This book offers an overview to the recently developed new ligands, new reaction conditions, and new apparatus to control the reactivity of nickel catalysts, allowing scientists to apply nickel catalysts to a variety of bond-forming reactions. A must-read for anyone working with organometallic compounds and their application in organic synthesis, this important guide: -Reviews the numerous applications of nickel catalysis in synthesis -Explores the use of nickel as a relatively cheap and earth-abundant metal -Examines the versatility of nickel catalysis in reactions like cross-coupling reactions and CH activations -Offers a resource for academics and industry professionals Written for catalytic chemists, organic chemists, inorganic chemists, structural chemists, and chemists in industry, Nickel Catalysis in Organic Synthesis provides a much-needed overview of the most recent developments in modern nickel catalysis and its application in synthesis.
Download or read book Development of Nickel catalyzed Cross electrophile Coupling of Aryl Chlorides and Triflates with Alkyl Halides written by Seoyoung Kim (Ph.D.) and published by . This book was released on 2023 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Cross-coupling is one of the most commonly used reactions in synthetic chemistry. While palladium-catalyzed cross-coupling is well-developed and established, cross-electrophile coupling is significantly younger field of study. In this approach two carbon electrophiles are directly coupled under reductive conditions, avoiding the need to prepare organometallic reagents. This is an attractive strategy because these reactions proceed through mild conditions, have high functional group tolerance, and employ readily available coupling partners. Nickel-catalyzed cross-electrophile couplings have seen considerable success in the past decade, initially in the coupling of organic iodides and later organic bromides. Despite these advances, the cross-coupling with the more abundant and inexpensive organic chlorides remain elusive due to their low reactivity. Furthermore the nickel-catalyzed cross-coupling of aryl triflates presents analogous challenges due to their differential reactivity. This thesis presents our studies to address these limitations. Through a combination of: (1) new ligand application, (2) fine tuning of alkyl electrophile reactivity through in situ halide exchange, (3) detailed mechanistic investigation of elementary steps, we demonstrate the nickel-catalyzed cross-electrophile coupling of these traditionally inert organic coupling partner. This dissertation is presented as follows: Chapter 1 is an introduction to cross-coupling strategies. Common palladium-catalyzed cross-coupling methods are discussed and their origin of cross-selectivity is highlighted. This is contrasted to cross-electrophile approaches of which mechanism is less well-understood. Early reports on nickel-catalyzed cross-electrophile coupling are presented and how mechanistic studies have elucidated the origin of cross-selectivity in these processes. Finally, the challenges of applying aryl chlorides in these first generation approaches are briefly discussed. Chapter 2 describes the development of nickel-catalyzed cross-electrophile coupling of aryl chlorides with primary alkyl chlorides to form C(sp2)-C(sp3) bonds. Investigation of ligands on selectivity and in situ halide exchange on the activation of C(sp3)-Cl bonds are detailed. Chapter 3 discusses a strategy for nickel-catalyzed cross-electrophile coupling of aryl triflates with alkyl halides. The development of reaction conditions for differing aryl electronics and mechanistic insights are described in detail. Mechanistically driven optimization and the extent of halide exchange to modulate alkyl halide reactivity are also discussed.
Download or read book Modern Organonickel Chemistry written by Yoshinao Tamaru and published by John Wiley & Sons. This book was released on 2006-03-06 with total page 346 pages. Available in PDF, EPUB and Kindle. Book excerpt: Organonickel chemistry plays an increasingly important role in organic chemistry, and interest in this topic is now just as keen as in organopalladium chemistry. While there are numerous, very successful books on the latter, a book specializing in organonickel chemistry is long overdue. Edited by one of the leading experts in the field, this volume covers the many discoveries made over the past 30 years, and previously scattered throughout the literature. Active researchers working at the forefront of organonickel chemistry provide a comprehensive review of the topic, including cross-coupling reactions, asymmetric synthesis and heterogeneous catalysis reaction types. A must-have for both organometallic chemists and synthetic organic chemists.
Download or read book Iron Catalysis written by Bernd Plietker and published by Springer Science & Business Media. This book was released on 2011-01-05 with total page 227 pages. Available in PDF, EPUB and Kindle. Book excerpt: Juan I. Padrón and Víctor S. Martín: Catalysis by means of Fe-based Lewis acids; Hiroshi Nakazawa*, Masumi Itazaki: Fe–H Complexes in Catalysis; Kristin Schröder, Kathrin Junge, Bianca Bitterlich, and Matthias Beller: Fe-catalyzed Oxidation Reactions of Olefins, Alkanes and Alcohols: Involvement of Oxo- and Peroxo Complexes; Chi-Ming Che, Cong-Ying Zhou, Ella Lai-Ming Wong: Catalysis by Fe=X Complexes (X=NR, CR2); René Peters, Daniel F. Fischer and Sascha Jautze: Ferrocene and Half Sandwich Complexes as Catalysts with Iron Participation; Markus Jegelka, Bernd Plietker: Catalysis by Means of Complex Ferrates.
Download or read book Development of Nickel Catalyzed Coupling Reactions written by Mikhail Olegovich Konev and published by . This book was released on 2017 with total page 503 pages. Available in PDF, EPUB and Kindle. Book excerpt: Transition metal catalyzed reactions are ubiquitous in the realm of synthetic chemistry, allowing for the strategic construction of complex molecular frameworks of pharmaceuticals, natural products, and synthetic materials. Palladium-catalyzed cross-coupling reactions are part of the foundation of these transformations, insofar as they were recognized with the 2010 Nobel Prize in chemistry. Traditionally, these reactions have relied on aryl and vinyl electrophiles, whereas the alkyl counterparts have only recently begun to emerge in the literature. Nickel has been on the forefront of enantioconvergent alkyl cross--coupling reactions due to its propensity to undergo single electron chemistry. However, under special conditions, it has a unique ability to break strong carbon--oxygen bonds in a stereospecific manner, making research into its reactivity a valuable endeavor to the field of organometallic chemistry.Chapter 1 describes the development of a stereospecific intramolecular alkyl-Heck cyclization of benzylic ethers. The reaction proceeds with inversion at the electrophilic carbon, for the synthesis of methylenecyclopentanes of both extended pi-electron and simple aromatic systems. The enantioenriched products can be effectively derivatized to cyclic alpha-aryl ketones in good yields with good transfer of chirality. Avenues to expand the utility of this reaction have been identified and further studies are ongoing.Chapter 2 discusses the development of nickel-catalyzed cross-electrophile coupling reactions of benzylic esters and aryl halides. An intermolecular reaction proceeds in high yields for primary benzylic esters for the synthesis of pharmacologically relevant diarylmethanes. The corresponding intramolecular cyclization proceeds under mild conditions, demonstrating the first example of a stereospecific cross-electrophile coupling of secondary benzylic esters. A variety of heterocyclic and functionalized substrates are tolerated under the reaction conditions.Chapter 3 examines the development a regio- and stereoselective nickel-catalyzed hydroarylation of alkynes with arylboronic acids. The reaction is facilitated by propargyl carbamates as directing groups. The reaction is tolerant of a range of functional groups and heterocycles. Mechanistic studies reveal that the acidic protons of the arylboronic acid coupling partner serve as the origin of hydrogen. Furthermore, the synthesis of tamoxifen can be completed in two steps from a simple hydroarylation product.
Download or read book Development of Stereospecific Nickel Catalyzed Cross Coupling and Reductive Cross Electrophile Coupling Reactions written by Lucas William Erickson and published by . This book was released on 2017 with total page 321 pages. Available in PDF, EPUB and Kindle. Book excerpt: In recent years, the Jarvo lab has developed the field of stereospecific nickel-catalyzed cross-coupling reactions of benzylic electrophiles. This chemistry allows for straightforward synthesis of asymmetric C--C bonds. The focus of this dissertation is on the study of the mechanism of these transformations, and the development of reductive cross-electrophile coupling reactions.First, the mechanism of the nickel-catalyzed Kumada cross-coupling reaction was studied via a 13C kinetic isotope effect experiment. This experiment indicated that oxidative addition of the nickel catalyst into the C--O sigma bond was the rate limiting step. Combining this data with a rate law allowed us to propose a catalytic cycle for this reaction. Additionally, the nickel-catalyzed deoxygenation of benzylic ethers was optimized for the formation of diaryl methanes. Deoxygenation performed best with a proton-rich Grignard reagent. We demonstrated that these Grignard reagents act as the hydride source for the reduction reaction.Next, an intramolecular nickel-catalyzed reductive cross-electrophile coupling reaction of benzylic ethers and alkyl chlorides was developed. This reaction proceeds with a variety of extended aromatic and heteroaromatic groups to produce cyclopropane rings in great yields and diastereoselectivity. This is the first example of a stereospecific reductive cross-electrophile coupling reaction, as well as the first to employ alkyl ethers and alkyl halides as the electrophiles.Finally, the work on nickel-catalyzed reductive cross-electrophile coupling reactions was expanded to synthesize vinylcyclopropanes from allylic ethers and alkyl halides. This reaction occurs with both alkyl fluorides and alkyl chlorides. To the best of our knowledge, this is the first reported cross-electrophile coupling reaction of an alkyl fluoride. Ring contraction proceeds with high stereospecificity, providing selective synthesis of either diastereomer of di- and tri-substituted cyclopropanes. The utility of this methodology is demonstrated by several synthetic applications including the synthesis of the natural product dictyopterene A. 2-Vinyl-4-fluorotetrahydrofurans also undergo stereospecific ring contractions, providing access to synthetically useful hydroxymethyl cyclopropanes.
Download or read book Nickel catalyzed Electrophile Cross coupling of Aryl Halides with Alkyl Halides written by Daniel A. Everson and published by . This book was released on 2013 with total page 264 pages. Available in PDF, EPUB and Kindle. Book excerpt: "This thesis details the author's contributions to the emerging field of electrophile cross-couplings. This new field is related to the well-established field of conventional cross-coupling that uses transition metal-catalysts to facilitate coupling reactions between electrophile-nucleophile pairs. Electrophile cross-coupling uses a conceptually different approach because it seeks to selectively join two different electrophiles with a transition metal-catalyst. The issue of developing cross-selective reactions is the central challenge addressed. Chapter 1 details recent advances and the state-of-the-art in conventional cross-coupling only for the purpose of conceptual comparison to electrophile cross-coupling. Additionally, a review of similar coupling reactions and their mechanisms are presented with the earliest examples of the unique reactivity that guided development of the reactions in this thesis. Chapter 2 details the first cross-selective nickel-catalyzed electrophile cross-coupling of iodoarenes with iodoalkanes. The new method displays exceptional functional group compatibility (-C(O)Me, -NHBoc, 1° and 2° alkyls, -OH) and the catalyst shows chemoselective reaction at C-I bonds over C-B bonds on bifunctional substrates. Mechanistic studies reveal that the reaction likely proceeds without the intermediacy of a carbon nucleophile, and that dimeric by-products arise from disproportionation of nickel intermediates. Chapter 2 also summarizes a detailed mechanistic study conducted in our lab that indicates the cross-coupled product is formed by a radical chain mechanism. Chapter 3 expands on the results of Chapter 2 by increasing the scope of the method to include bromo- and chloroarenes for the first time. Additional competition experiments reveal that the new catalysts and reaction conditions are chemoselective for the cross-coupling of two electrophilic C-Br bonds over conventional cross coupling of C-Br bonds with C-B, C-Sn, or C-Si bonds. Further mechanistic work reveals that [upsilon] [is proportional to] [bromoalkane][^x][catalyst][^y]/[bromoarene][^z] (x, y, and z are positive numbers and could be non-integers). Chapter 4 presents the first electrophile cross-couplings of halogenated pyridines with alkyl bromides. Scope and limitations are discussed in the context of improving the method. Chapter 5 details the effect of additives on other related electrophile coupling reactions"--Pages vii-viii.
Download or read book Transition Metal catalyzed Cross coupling of Silicon Electrophiles for the Synthesis of Vinyl and Alkyl Silanes written by Andrew Patrick Cinderella and published by . This book was released on 2018 with total page 533 pages. Available in PDF, EPUB and Kindle. Book excerpt: Vinyl and alkyl silanes are important molecules in organic synthesis, medicinal chemistry, and materials chemistry. The ability of vinyl silanes to participate in Hiyama-Denmark cross-coupling, oxidations, and desilylative halogenations make them highly versatile intermediates. Alkyl silanes engage in similar oxidations and Peterson olefinations. The material properties of alkyl silanes are still under exploration, but they display a profound propensity for freezing point depression when compared to hydrocarbon congeners and amplified lipophilicity of bioactive molecules. I sought to develop methods that could synthesize vinyl and alkyl silanes through transition metal catalysis. Prior to this work, there were limited methods to access vinyl silanes from silyl triflates and secondary alkyl silanes from halosilanes and an organometallic nucleophile. ☐ This dissertation describes the discovery and development of transition metal catalyzed methods to form vinyl and alkyl silanes. We have developed a nickel-catalyzed silyl Heck reaction capable of activating silyl triflates with iodide additives. This methodology allows the first access to silyl triflate electrophiles in cross-coupling, greatly expanding the scope and capabilities of the silyl-Heck reaction. ☐ Advancing the utility of transition metal-catalyzed cross-coupling of halosilanes, I was able to develop a high yielding methodology for the synthesis of secondary alkyl silanes from organozinc halides and iodosilanes; formally a silyl-Negishi reaction. This alkylation strategy was then improved upon by the discovery and development of chlorosilane cross-coupling of Grignard reagents. Exploration of this unprecedented chlorosilane cross-coupling revealed that highly sterically hindered secondary alkyl silanes were capable of being accessed with this methodology. Additionally, mechanistic studies suggest against a typical Kumada cross-coupling mechanism and favor the formation of anionic palladium to perform a substitution at the silicon center.
Download or read book Applied Cross Coupling Reactions written by Yasushi Nishihara and published by Springer Science & Business Media. This book was released on 2012-12-14 with total page 247 pages. Available in PDF, EPUB and Kindle. Book excerpt: “Applied Cross-Coupling Reactions” provides students and teachers of advanced organic chemistry with an overview of the history, mechanisms and applications of cross-coupling reactions. Since the discovery of the transition-metal-catalyzed cross-coupling reactions in 1972, numerous synthetic uses and industrial applications have been developed. The mechanistic studies of the cross-coupling reactions have disclosed that three fundamental reactions: oxidative addition, transmetalation, and reductive elimination, are involved in a catalytic cycle. Cross-coupling reactions have allowed us to produce a variety of compounds for industrial purposes, such as natural products, pharmaceuticals, liquid crystals and conjugate polymers for use in electronic devices. Indeed, the Nobel Prize for Chemistry in 2010 was awarded for work on cross-coupling reactions. In this book, the recent trends in cross-coupling reactions are also introduced from the point of view of synthesis design and catalytic activities of transition-metal catalysts.
Download or read book Nickel catalyzed Reductive Coupling of Alkyl Allyl and Vinyl Electrophiles written by Michael R. Prinsell and published by . This book was released on 2013 with total page 187 pages. Available in PDF, EPUB and Kindle. Book excerpt: "The nickel-catalyzed reductive coupling of two organic electrophiles to form new carbon-carbon bonds is a fast emerging field of chemistry, with applications to the synthesis of medicinally interesting compounds. This method is an alternative to traditional transition metal-catalyzed cross-coupling reactions of organic electrophiles with organometallic nucleophiles. This thesis details the author's work towards the development of several reactions to reductively couple organic molecules to form Csp3-Csp3 bonds, including alkyl, allyl and vinyl halides. Chapter 1 delves into the background of traditional metal-catalyzed crosscoupling reactions as well as the advantages and challenges associated with using a reductive method to construct C-C bonds. In particular this chapter presents the specific challenges associated with the formation of a carbon-carbon bond between two Csp3 hybridized carbons. Chapter 2 outlines the development of a mild, general dimerization reaction of alkyl halides. This chapter also focuses on the use of sodium iodide to extend the coupling to molecules that are unreactive to the standard reaction conditions. Chapter 3 details work towards the cross-coupling of two alkyl halides. While cross-selectivity remains a challenge, some potential solutions are discussed. Chapter 4 presents the optimization and reaction scope of the coupling of allyl acetates with secondary alkyl halides, as well as progress towards couplings with primary alkyl halides. In addition, the first report of the catalytic coupling of vinyl bromides with allyl acetates is reported. Chapter 5 focuses on work towards the reductive cyclization of alkyl halides and allyl acetates. Initial results show promising diastereomeric ratios. Chapter 6 details work on the dehydrogenative synthesis of bipyridine and terpyridine ligands. These ligands are useful and are used for many reductive coupling reactions in the Weix group"--Pages vi.
Download or read book Nickel catalyzed Asymmetric Cross couplings of Secondary Alkyl Electrophiles and Photoinduced Copper catalyzed C N Couplings written by Junwon Choi (Ph. D.) and published by . This book was released on 2014 with total page 361 pages. Available in PDF, EPUB and Kindle. Book excerpt: Chapter 1 describes the development of three nickel-catalyzed asymmetric Negishi cross-couplings of secondary alkyl electrophiles via a stereoconvergent process. In Section 1.1, asymmetric Negishi arylations and alkenylations of [alpha]-bromonitriles with arylzinc and alkenylzinc reagents are achieved using a nickel/bis(oxazoline) catalyst. Section 1.2 describes stereoconvergent cross-couplings of secondary unactivated alkyl electrophiles, specifically, Negishi arylations and alkenylations of [alpha]-bromosulfonamides and abromosulfones with arylzinc reagents and alkenylzirconium reagents, respectively. Section 1.3 details progress toward asymmetric cross-couplings between [alpha]-haloboronate esters and alkylzinc reagents using a nickel/diamine catalyst. Chapter 2 describes the development of photoinduced, copper-catalyzed C-N couplings between N-heterocycles and aryl halides. In particular, a variety of N-heterocycles, such as indoles, benzimidazoles, imidazoles, and carbazoles, undergo Ullmann couplings under mild conditions (room temperature) with an inexpensive catalyst (Cul, without an added ligand).
Download or read book The Stille Reaction written by Vittorio Farina and published by John Wiley & Sons. This book was released on 1998-09-18 with total page 676 pages. Available in PDF, EPUB and Kindle. Book excerpt: Die Stille-Reaktion ist eine der sehr wenigen Reaktionen, in denen unter milden Bedingungen Kohlenstoff-Kohlenstoff-Bindungen geknüpft werden können. Man verwendet die Reaktion häufig in der Synthese komplizierter Moleküle zur Verknüpfung größerer Molekülbausteine. Die Autoren diskutieren vom präparativen Standpunkt aus Grenzen, Einflüsse, strukturelle Effekte und die Wahl der geeigneten Reaktionsbedingungen. Mit ausführlichen Vorschriften und vielen Beispielen. (11/98)
Download or read book Exploring Ligand Enabled Nickel Catalyzed Cross Coupling of Sulfur Based Nucleophiles written by Connor Simon and published by . This book was released on 2022 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: The catalytic synthesis of C(sp2)-N linkages is of utmost significance in modern synthetic chemistry, predominantly due to their prevalence in active pharmaceutical ingredients and natural products. Pd-catalyzed cross-couplings of this type, known colloquially as Buchwald-Hartwig amination (BHA), represent a tremendously important class of reactions in research and industrial settings. The success achieved by BHA can largely be attributed to the rational design of ancillary ligands specifically configured to exploit the natural electronic characteristics of the Pd metal centre. Research efforts surrounding the BHA reaction have enabled the scope of suitable coupling partners to grow rapidly, encompassing a vast array of (hetero)aryl (pseudo)halides and NH couplings partners. Notwithstanding the value of the BHA reaction, concerns over the rising costs of Pd and subsequent sustainability issues have prompted researchers to seek economical methods for accessing these linkages. One of the most promising alternatives to Pd-catalysis is the developing field of its 3d congener, Ni. However, given the relatively underdeveloped nature of Ni-catalyzed C-N bond formation, many questions regarding the mechanistic underpinnings and scope limitations remain unanswered. In this thesis, my contributions include experimental investigations into the elementary steps of a successful Ni-catalyzed cross-coupling. The successful synthesis and characterization of primary Ni-NHR catalytic intermediates reveal previously undocumented C-N bond-forming pathways, and the implementation of the mechanistic lessons learned from these studies allow for the discovery of new ligand-enabled Ni-catalyzed C-N cross-couplings.
