C-C Cross Couplings with 3d Base Metal Catalysts
- 2023
- Book
- Editor
- Xiao-Feng Wu
- Book Series
- Topics in Organometallic Chemistry
- Publisher
- Springer International Publishing
About this book
This volume presents recent progress on 3d base metal catalyzed C-C cross coupling reactions. The contributions provide detailed discussions on the use of cheap metal catalysts such as Cr, Mn, Fe, Co, Ni, Cu, and Zn to construct Csp2-Csp2, Csp2-Csp3 and Csp3-Csp3 bonds with a variety of substrates. These non-noble metal catalyst have many advantages such as being inexpensive, having low toxicity and are environmentally benign. Therefore the use of cheap metal catalysts in organic synthesis has gained much attention in efforts to develop more sustainable synthetic green chemistry. Each chapter is written by international experts in the field and is a great resource for students, researchers and chemists working in industry to gain an overview on the latest developments.
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Table of Contents
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Frontmatter
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C–C Cross Couplings with Chromium Catalysis
Yunqian Hou, Wen Xu, Xiaoming ZengThis chapter delves into the underdeveloped field of chromium-catalyzed cross couplings of C–C bonds, despite chromium's abundance and low cost. It discusses the catalytic activities of chromium in cross couplings, particularly focusing on the use of low-valent chromium species to promote two-electron oxidative addition and reductive elimination. The chapter highlights recent advancements in the Kumada coupling of unactivated C–O, C–N, and C–S bonds, as well as cross-electrophile couplings of C–O and C–N bonds. It also explores the challenges and future directions in this area, including the need for structurally defined low-valent chromium complexes and the expansion of chromium catalysis to other σ-bonds. The chapter aims to attract more attention from the synthetic community to contribute to this emerging field.AI Generated
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AbstractChromium is one of the earth-abundant transition metals. The use of chromium as low-cost alternative to precious metals for catalysis is of great synthetic and mechanistic interest. Progress in the development of cross-coupling reactions by chromium catalysis has been recently made, offering valuable strategies to forge C–C bonds under mild conditions. This chapter aims to highlight recent achievements in the development of strategies for constructing ubiquitous C–C bonds through chromium catalysis in recent years. It is organized by cross couplings with chemically inert C–heteroatom and C–H bonds in forming C–C bonds, mainly focusing on the discussion of plausible mechanisms for insight into design of robust catalysts, as well as the development of new coupling models and catalytic strategies. -
Mn-Catalyzed C–C Coupling Reactions
Yunhui Yang, Congyang WangThis chapter delves into the significant progress made in manganese-catalyzed C-C coupling reactions, particularly focusing on C-H activation and hydrocarbofunctionalization of unsaturated C-C bonds. Over the past decade, manganese has emerged as a sustainable and cost-effective alternative to noble metal catalysts, driving innovations in organic synthesis. The chapter covers various transformations, including C-H activation of inert C-H bonds, addition to polar and nonpolar bonds, and cyclization reactions. Notably, it highlights the unique reactivity and redox-neutral pathways of manganese catalysis, making it an invaluable resource for experts in organic chemistry and catalysis.AI Generated
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AbstractManganese-catalyzed C–C bond coupling reactions are such an attractive alternative tool for the synthesis of organic functional molecules that they are gained considerable attention in the last decade. This chapter highlights selected examples of the recent advances in the catalytic functionalization of inert Csp2–H bonds through organometallic C–H activation. Reactions involving the hydrocarbofunctionalization of unsaturated C–C bonds leading to C–C bonds formation are also briefly addressed herein. -
Iron-Catalyzed Carbon–Carbon Coupling Reaction
Qiao Zhang, Shou-Fei ZhuThe chapter delves into the significant advancements in iron-catalyzed carbon–carbon coupling reactions over the past two decades, focusing on their advantages over palladium and nickel complexes. It discusses various types of coupling reactions, including C(sp2)─C(sp3), C(sp2)─C(sp2), C(sp3)─C(sp3), C(sp2)─C(sp), and C–H direct coupling. The chapter also explores the mechanisms behind these reactions, the challenges faced, and the potential for future applications in industrial production. The text is particularly noteworthy for its detailed review of the literature and its emphasis on the practical and economic benefits of iron catalysis.AI Generated
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AbstractTransition metal-catalyzed coupling reaction is one of the most effective strategies to construct carbon–carbon bonds. Because iron is Earth abundant and environmental benign, the Fe-catalyzed carbon–carbon coupling reactions have attracted extensive attention in the past two decades. A variety of iron catalysts have been developed to realize cross-coupling of electrophilic and nucleophilic reagents, oxidative coupling, reductive coupling, and C–H bond direct coupling reactions. The asymmetric carbon–carbon coupling reactions have also been successfully achieved using chiral iron catalysts. This chapter reviews the recent research progress of Fe-catalyzed carbon–carbon coupling reaction, mainly from the perspective of the type of newly formed carbon–carbon bonds, reaction conditions, substrate types, and reaction mechanisms. -
Cobalt-Catalyzed C–C Coupling Reactions with Csp3 Electrophiles
Jie LiThis chapter delves into the significant advances in cobalt-catalyzed carbon-carbon bond formation with Csp3 electrophiles, a critical area in synthetic organic chemistry. It discusses various strategies for these reactions, including cross-couplings with organometallic reagents, reductive cross-couplings, and direct C–H activations. Notably, the chapter covers the use of cobalt catalysts in coupling alkyl halides with organomagnesium reagents, allylic acetates, and other electrophiles. The text also highlights the development of enantioselective cobalt-catalyzed cross-couplings and the potential applications of these methodologies in the synthesis of bioactive compounds. Additionally, it explores the use of cobalt catalysis in other cross-coupling reactions, such as those involving organozinc reagents, manganese, aluminium, and boron-based reagents. The chapter concludes by emphasizing the sustainable and versatile nature of cobalt catalysis in organic synthesis, setting the stage for future developments in this field.AI Generated
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AbstractCarbon–carbon bond construction is a long-standing challenge in synthetic organic chemistry. In the recent years, transition-metal-catalyzed C–C bond forming reactions have emerged as a powerful tool in the synthesis of pharmaceuticals, agrochemicals, natural products, and feedstock commodity chemicals. Among them, the inexpensive 3d cobalt catalysts have received special attention due to their low cost and high activity in C–C coupling reactions, which experienced a remarkable progress during the past decades. Herein, recent advances in the field of organometallic cobalt-catalyzed C–C coupling reactions with Csp3 electrophiles are reviewed until July 2022. -
Co-catalyzed C–C Coupling Reactions with Csp2 Electrophiles
Corinne Gosmini, Mengyu GaoThe chapter delves into the significance of cobalt-catalyzed cross-coupling reactions, particularly with Csp2 electrophiles, in organic synthesis. It discusses the advantages of cobalt over palladium, including lower cost and reduced toxicity, and highlights key methods and applications. The text covers various types of organometallic reagents, including Grignard reagents, organozinc reagents, and organoboron reagents. It also explores reductive cross-coupling reactions, which avoid the use of stoichiometric organometallic species, making the process more sustainable. The chapter emphasizes the versatility of cobalt catalysts in forming Csp2–Csp2, Csp2–Csp3, and Csp2–Csp bonds, and provides insights into the mechanisms and practical applications of these reactions.AI Generated
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AbstractTransition metal-catalyzed formation of C–C bonds was one of the most important methods in chemical synthesis since the pioneering work of Heck, Negishi, and Suzuki. Now, cross-coupling reactions involving Csp2 electrophiles are commonplace in both industrial and academic research. With the development in this field, cheap and less toxicologically benign cobalt catalyst attracted more and more attention, and displays a high catalytic activity in many cases and a low tendency to produce homocoupling and β-elimination by-products. In this chapter, we will introduce the Co-catalyzed cross-coupling of Csp2 electrophiles with organometallic reagents (like Grignard reagent, organozinc, organoboron, etc.) to construct Csp2–C bonds, as well as the Co-catalyzed reductive cross-couplings involving two electrophiles. -
Recent Advances in Nickel-Catalyzed C-C Cross-Coupling
Yangyang Li, Jiao Long, Guoyin YinThe chapter delves into the significant advances in nickel-catalyzed cross-coupling reactions, a powerful tool in synthetic applications. It begins by discussing the discovery and unique properties of nickel in catalyzing cross-coupling reactions, comparing it to palladium. The text then explores various catalytic strategies, including classical, reductive, oxidative, and C-H activation cross-coupling reactions. It highlights key mechanisms, such as the activation of electrophiles and the reduction potential of nickel. The chapter also covers recent developments in nickel-catalyzed cross-coupling, including the construction of biheteroaryls, the synthesis of bioactive agents, and the application of chain-walking. Additionally, it discusses the challenges and future directions in this field, making it a must-read for those interested in the latest developments in nickel-catalyzed cross-coupling reactions.AI Generated
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AbstractTransition metal-catalyzed carbon–carbon bonds formation is a fundamental process and has attracted much attention in the synthetic chemistry community over the past decades. This chapter summarizes the recent advances (from 2012 until 2022) in nickel-catalyzed C-C coupling reactions, covering the formation of C(sp2)-C(sp2) bond, C(sp2)-C(sp3) bond, and C(sp3)-C(sp3) bond, as well as the corresponding innovative strategies and mechanisms are discussed in detail, with an emphasis on nickel’s unique properties. -
Copper-Catalyzed C–C Bond Formation via Carboxylation Reactions with CO2
Zhengkai Chen, Xiao-Feng WuThe chapter delves into the crucial role of copper-catalyzed carboxylation reactions with CO2 in synthesizing carboxylic acids and their derivatives, emphasizing their importance in organic synthesis, chemical industry, agrochemicals, and pharmaceuticals. It discusses the advantages of using CO2 as a C1 feedstock and the challenges posed by its thermodynamic stability and kinetic inertness. The chapter highlights the significant advancements in copper-catalyzed carboxylation reactions, including the use of various substrates such as organometallic reagents, organosilane reagents, and organoaluminum reagents. It also explores the carboxylation of C–C double bonds, C–C triple bonds, and C–H bonds, showcasing the versatility and potential of copper catalysts in these transformations. The chapter concludes by emphasizing the need for further research to develop more efficient and practical methodologies for the large-scale production of carboxylic acids using CO2.AI Generated
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AbstractC–C bonds are ubiquitous in the skeleton of natural products, drugs, materials, ligands, and various bioactive molecules. Transition metal-catalyzed carboxylation reactions with abundant CO2 provide a direct and efficient method to forge C–C bonds, thereby producing various valuable carboxylic acids and their derivatives. Compared with other transition metal catalysts, copper catalysts have the merits of easy availability, low toxicity, and unique catalytic activity. This chapter systematically overviews the development of copper-catalyzed carboxylation reactions with CO2 to realize the formation of C–C bonds based on the type of the reactive substrates. -
Cu-Catalyzed C–C Bond Formation with CO
Pinku Tung, Neal P. MankadThis chapter delves into the burgeoning field of copper-catalyzed carbonylation reactions, focusing on the formation of C–C bonds using CO. It begins by discussing the ubiquity of carbonyl compounds in various organic scaffolds and their critical roles in functional properties. Traditionally synthesized using precious metals like rhodium and palladium, these reactions are now seeing a renewed interest in using first-row transition metals like copper due to their earth abundance and unique mechanistic pathways. The chapter organizes these reactions by the type of nucleophile involved, including carbon, hydride, boron, and nitrogen nucleophiles. It covers key transformations such as hydroxymethylation, carbonylative borylation, and carbonylative cross-coupling reactions. Notably, it highlights the advantages of copper catalysis in terms of sustainability and the potential for new reaction discovery. The chapter also discusses recent advancements in radical cascade reactions and the synthesis of complex molecules, showcasing the versatility and promise of copper-catalyzed carbonylation in modern organic synthesis.AI Generated
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AbstractConstruction of C–C and C–X bonds via carbonylation provides an attractive strategy to synthesize carbonyl compounds such as ketones, amides, esters, and carboxylate derivatives at mild and atom-economical reaction conditions. To complement historic progress in noble metal-catalyzed carbonylation, more sustainable avenues involving earth-abundant metals are actively being investigated. Copper has recently emerged as one of the most suitable metals with unique catalytic carbonylation reactivity. Here, we provide a comprehensive review of carbonylative C–C coupling and cover selected examples of carbonylative C–X coupling catalyzed by copper. The contents have been divided based on the nucleophiles applied in carbonylative coupling with carbon-centered electrophiles. Discussions of substrate scope and mechanisms are included. -
Cu-Catalyzed C-C Coupling Reactions
Manjunath S. Lokolkar, Yuvraj A. Kolekar, Prafull A. Jagtap, Bhalchandra M. BhanageThe chapter delves into the historical and contemporary significance of copper-catalyzed C-C coupling reactions, which have revolutionized synthetic organic chemistry. It begins with an introduction to the transition metal-catalyzed cross-coupling strategies, emphasizing the role of copper in forming carbon-carbon and carbon-heteroatom bonds. The chapter then explores the untapped potential of copper catalysts in various coupling reactions, including those involving terminal alkynes, Grignard reagents, organozinc reagents, and organosilicon reagents. It also discusses the classical cyanation reactions and their modifications, as well as aryl-aryl bond formation through copper-catalyzed alkenylation, alkynylation, and allylation reactions. The chapter concludes by highlighting the unique advantages of copper catalysts, such as their low cost, high earth abundance, and environmental benignity, making them a sustainable alternative to noble metal catalysts.AI Generated
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AbstractThis book chapter intends to give the reader a timely overview of significant copper-catalyzed cross-coupling reaction advancements. Carbon–carbon bond formation through cross-coupling methodologies is among the most indispensable and versatile tools in organic synthesis for constructing the carbon framework of organic molecules. The uncontested role of the expensive and less-abundant 2d and 3d row metals for organic and organometallic synthesis is evident based on their exceptional catalytic performance and high industrial demand. These applications can cause environmental and economic concerns, which can be alleviated by replacing these metals by applying the highly abundant and cost-effective 1d transition metals. Copper-based catalysts are an attractive choice for emerging new synthetic methodologies due to their relatively lower toxicity, low cost, and high catalytic activity. In this context, this chapter intends to develop an understanding of novel and sustainable strategies and methodologies in organic and organometallic chemistry by utilizing the concepts elaborated in detail below for carbon–carbon bond formation, which is vital for future synthesis design. This chapter covers protocols in copper-catalyzed Csp3-Csp3, Csp3-Csp2, Csp3-Csp, Csp2-Csp2, and Csp-Csp bonds formation through several strategies such as Ullmann-type reaction, cross-coupling with organometallic reagents, cyanation, alkynylation, alkenylation, allylation reactions, and oxidative cross-coupling reactions. Moreover, a brief description of direct C-H functionalization referred to as cross-dehydrogenative coupling (CDC) for direct carbon–carbon bond formation has been summarized.Graphical AbstractFull size image -
Zinc-Catalyzed C-C Coupling Reactions
C. M. A. Afsina, Thaipparambil Aneeja, Gopinathan AnilkumarThis chapter delves into the significant role of zinc in catalyzing various C-C coupling reactions, a crucial process in organic synthesis. It discusses the advantages of zinc over other transition metals, such as its low toxicity and cost-effectiveness. The chapter covers a range of zinc-catalyzed reactions, including Sonogashira, Suzuki, Cadiot–Chodkiewicz, and cross-dehydrogenative couplings. Notably, it highlights recent innovations like nanomagnetic zinc catalysts and visible light-mediated methods. The chapter also underscores the need for further research into the mechanistic aspects and recyclability of zinc catalysts. Overall, this chapter offers a compelling exploration of the current state and future potential of zinc-catalyzed C-C coupling reactions in various industries.AI Generated
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AbstractCross-coupling reactions have emerged as one of the most powerful tools for the formation of carbon–carbon and carbon–heteroatom bonds. In the past few years, enormous efforts have been made in developing efficient 3d transition metal catalyzed cross-coupling reactions. Among the different metals, zinc has great potential owing to its non-toxicity, earth abundance, eco-friendly, and inexpensive characteristics. During the last three decades, large number of reports have been disclosed employing zinc salts as catalysts. In view of the great interest in cross-coupling reactions, in this chapter, we summarize the chemistry to give an overview of zinc-catalyzed C-C cross-coupling reactions. -
Correction to: C-C Cross Couplings with 3d Base Metal Catalysts
Xiao-Feng WuThe chapter addresses a critical correction in the volume number of 'C-C Cross Couplings with 3d Base Metal Catalysts', a significant resource in the field of organometallic chemistry. This correction is vital for maintaining the accuracy of citations and references, ensuring that researchers can rely on the correct volume number when delving into the detailed discussions on C-C cross couplings catalyzed by 3d base metal catalysts. The chapter underscores the importance of precision in academic publications and highlights the necessity of prompt corrections to avoid any potential misinterpretations or misattributions in scientific literature.AI Generated
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- Title
- C-C Cross Couplings with 3d Base Metal Catalysts
- Editor
-
Xiao-Feng Wu
- Copyright Year
- 2023
- Publisher
- Springer International Publishing
- Electronic ISBN
- 978-3-031-32867-1
- Print ISBN
- 978-3-031-32866-4
- DOI
- https://doi.org/10.1007/978-3-031-32867-1
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