Iridium Catalysts for Organic Reactions
- 2021
- Book
- Editors
- Prof. Dr. Luis A. Oro
- Prof. Dr. Carmen Claver
- Book Series
- Topics in Organometallic Chemistry
- Publisher
- Springer International Publishing
About this book
This new volume “Iridium Catalysts for Organic Reactions” in the series “Topics in Organometallic Chemistry” intends to update several representative well-known reactions and to introduce other less known or new reactions in particular covering sustainability aspects. Iridium complexes are efficient in many catalytic homogeneous transformations providing high efficiency in both results, activity and selectivity. The interest of the book lies in the presentation of the advances, new perspectives and application in a variety of representative iridium-catalysed reaction. All chapters in the volume are contributed by relevant international experts in the field. The book is aimed at researchers, graduate students and synthetic chemists at all levels in academia and industry.
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Table of Contents
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Frontmatter
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Iridium-Catalyzed Dehydrogenative Reactions
Takuya Shimbayashi, Ken-ichi FujitaThe chapter delves into the maturity of iridium catalysis in organic synthesis, particularly focusing on dehydrogenative reactions. It begins with an introduction to the fundamental reactions catalyzed by iridium, such as oxidative addition and hydrogenation. The text then explores the development of iridium catalysts for dehydrogenative transformations, including the dehydrogenation of alkanes and cycloalkanes. Notably, it discusses the use of pincer ligands to enhance catalyst stability and activity. Additionally, the chapter covers iridium-catalyzed borylation of hydrocarbons, which has become a significant area of research due to the ease of handling and functional group compatibility of organoboronates. The chapter concludes by highlighting the potential of iridium catalysis in various dehydrogenative transformations, making it a valuable resource for researchers in the field of catalysis and organic synthesis.AI Generated
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AbstractThis chapter summarizes the recent advances in homogeneous iridium complex-catalyzed dehydrogenative reactions, covering the dehydrogenation of alkanes, heterocyclic compounds, alcohols, and formic acid. Both simple reactions affording unsaturated products and relatively sophisticated organic transformations triggered by substrate dehydrogenation are discussed, and many of the listed catalytic systems are revealed to have become important tools for organic synthesis. -
Recent Advances in Iridium-Catalysed Transfer Hydrogenation Reactions
M. Pilar Lamata, Vincenzo Passarelli, Daniel CarmonaThe chapter 'Recent Advances in Iridium-Catalysed Transfer Hydrogenation Reactions' delves into the latest developments in the field of transfer hydrogenation reactions using iridium catalysts, with a focus on the period from 2015 to 2020. It begins by introducing the concept of transfer hydrogenation and its significance, tracing back to the pioneering work of Meerwein and Verley in 1925. The chapter then explores the evolution of the transfer hydrogenation reaction, including the incorporation of transition metal compounds in the 1960s and the groundbreaking work of Noyori and co-workers in the 1990s. The text covers various types of ligands used in iridium complexes, such as pentamethylcyclopentadienyl, carbene, pincer, and other ligands, and their applications in transfer hydrogenation. It also discusses the expansion of the scope of substrates and the development of more abundant and sustainable transition metal catalysts. The chapter is structured to classify the results obtained according to the type of ligand and includes subsections on the transfer hydrogenation of CO2, water, biological systems, and other relevant topics. The chapter concludes by emphasizing the remarkable features and achievements in the field of iridium-catalysed transfer hydrogenation reactions, making it a valuable resource for specialists in catalysis and chemical research.AI Generated
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AbstractThis review focuses on the contributions of the last 5 years to the application of iridium complexes as homogeneous catalysts in transfer hydrogenation (TH) reactions. The reduction of carbonyls, imines, alkenes and alkynes is considered. The TH of unsaturated alkene-carbonyl substrates and heterocycles is particularly studied. Recent results on the reduction of CO2 are also included. Special attention is paid to THs performed in aqueous medium as well as to the development of TH in biological media. The employ of biomass-derived products as reagents or solvents in TH transformations is also reviewed. Finally, the proposed mechanisms for TH reactions are revised. -
Iridium-Catalyzed Asymmetric Hydrogenation
Jèssica Margalef, Oscar Pàmies, Montserrat DiéguezAbstractIn this chapter, we describe the development in homogeneous Ir-catalyzed asymmetric hydrogenation with particular emphasis on the achievements made during the last 10 years. We also present their application to the synthesis of complex molecules. The first section deals with the hydrogenation of unfunctionalized olefins or with poorly coordinative groups. The second section includes the advances made in the hydrogenation of functionalized olefins. The last two sections cover the hydrogenation of imines and ketones, respectively. -
Iridium-Catalyzed Undirected Homogeneous C–H Borylation Reaction
Elena FernándezThe chapter delves into the latest advances in iridium-catalyzed undirected homogeneous C–H borylation reactions, with a focus on substrates such as heteroarenes, arenes, and alkanes. It explores the mechanisms behind these reactions, including the accepted catalytic cycle based on Hartwig's experimental studies. The chapter also discusses the various catalysts and ligands used, such as [Ir(μ-Cl)(COD)]2, [Ir(μ-OMe)(COD)]2, and [Ir(η6-mes)(Bpin)3], and their modifications. Additionally, it highlights the relevance of these reactions in achieving high selectivity without the need for directing groups. The chapter provides a detailed analysis of the borylation of heteroarenes, arenes, and alkanes, including the influence of different ligands and substrates on regioselectivity. It also covers the development of new catalytic systems and the use of theoretical calculations to understand the reaction mechanisms. The chapter concludes with a discussion on the future challenges and potential directions in the field of iridium-catalyzed C–H borylation.AI Generated
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AbstractThe present chapter describes the intense efforts devoted to develop new concepts from 2014 up today in the iridium-catalyzed undirected homogeneous C–H borylation of heteroarenes, arenes, and alkanes. Selectivity issues are principally highlighted in this chapter since no directed groups are included in these approaches, but improved ligands are responsible of the new trends instead. In parallel, mechanistic insights on the C–B bond formation analyzed through density functional theory orientate the suggestion of alternative catalytic cycles, to understand the high level of selectivity on Csp2-H and Csp3-H borylation. This area of work keeps very active because of the inherent interest on the C–B bond formation allowing access to multifunctionalized products, in a straightforward manner. -
Iridium-Catalyzed Silylation
Manuel Iglesias, Luis A. OroThis chapter delves into the significant advancements in iridium-catalyzed silylation processes, a cornerstone in the synthesis of organosilanes. It begins with an introduction to the importance of organosilanes in materials science and organic synthesis, emphasizing their versatile reactivity. The chapter then focuses on the hydrosilylation of unsaturated bonds, including ketones, alkenes, alkynes, and cyclopropanes, showcasing the selectivity and efficiency of iridium catalysts. Notably, it discusses the inversion of absolute configuration observed in the hydrosilylation of ketones catalyzed by iridium compared to rhodium. The chapter also explores dehydrogenative silylation reactions, which enable the functionalization of C–H bonds in alkanes, arenes, and heteroarenes, demonstrating the potential of these methods for the synthesis of complex molecules. Throughout, the chapter provides insights into the reaction mechanisms and highlights the unique properties of iridium catalysts, making it a valuable resource for researchers and professionals in the field of organic synthesis and catalysis.AI Generated
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AbstractIn this chapter, homogeneous iridium-catalyzed silylation reactions are reviewed, focusing primarily on their synthetic utility. Additionally, relevant catalytic cycles are commented, paying especial attention to those that are more representative of each type of process. The chapter is divided into two main types of reactions, namely, hydrosilylation and C–H bond silylation. The former deals with the hydrosilylation of polar unsaturated bonds (ketones and imines) and non-polar unsaturated bonds (alkenes and alkynes). The latter covers the directed and non-directed C–H bond silylation of alkenes, alkynes, arenes, and alkanes – mainly comprising dehydrogenative silylation reactions, which may occur in the presence or absence of a hydrogen acceptor. -
Iridium Catalysts for Hydrogen Isotope Exchange
Marc ReidThe chapter delves into the use of iridium catalysts for hydrogen isotope exchange (HIE), a crucial process in the synthesis of isotopically labeled compounds. It covers the fundamentals of isotopic labeling, the importance of HIE in pharmaceutical research, and the development of various synthetic methods for HIE. The chapter also provides a detailed mechanistic analysis of iridium-catalyzed HIE, highlighting the role of different ligands and catalyst structures in determining the selectivity and efficiency of the reaction. Additionally, it discusses the applications of HIE in mass spectrometry and the challenges associated with labeling complex organic molecules. The chapter concludes with a summary of recent advancements in the field and the potential for future developments in iridium-catalyzed HIE.AI Generated
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AbstractA history and summary of iridium-catalyzed hydrogen isotope exchange (HIE) is described. Owing to the wide range of applications served by installation of heavy and radioactive hydrogen isotopes, a wealth of synthetic labeling strategies have been forthcoming. Principle among all HIE methods are those developed using homogeneous iridium catalysts. This chapter covers major developments in (primarily homogeneous) iridium-centered catalysts for HIE. Connections to the broader fields of hydrogenation and C–H functionalization are also considered. -
Iridium-Catalyzed Homogeneous Hydrogenation and Hydrosilylation of Carbon Dioxide
Francisco J. Fernández-Alvarez, Luis A. OroThe chapter explores the significance of carbon dioxide as a chemical feedstock and the challenges associated with its thermodynamic stability. It focuses on the progress made in iridium-catalyzed reduction of CO2 using hydrogen and hydrosilanes, highlighting the efficiency and selectivity of iridium complexes in producing formic acid, methanol, and other valuable chemicals. The chapter also delves into the mechanisms of CO2 activation and the potential of iridium catalysts in sustainable chemical processes, making it a valuable resource for researchers and professionals in the field of catalysis and green chemistry.AI Generated
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AbstractThe knowledge of the potential of transition metal-based complexes as catalysts for the reduction of CO2 has grown significantly over the last few decades. This chapter focuses on the progress made during recent years in the field of homogeneous iridium-catalyzed reduction of CO2 by using hydrogen and/or silicon hydrides as reducing agents, comparing them with homogeneous catalysts based on other transition metals.The reported studies on iridium-catalyzed CO2 reduction processes show that an important point to keep in mind when designing a catalyst is the nature of the reducing agent (hydrogen, hydrosilanes, and/or hydrosiloxanes). Thus, iridium(III) half-sandwich complexes with 4,4′-dihydroxy-bipyridine (DHBP) or 4,7-dihydroxy-1,10-phenanthroline (DHPT) ligands, and iridium(III)-PNP pincer complexes have proven to be excellent catalysts for the hydrogenation of CO2 to formic acid. However, Ir(III)-NSiNMe (NSiN = fac-bis-(4-methylpyridine-2-yloxy)methylsilyl) and Ir(III)-NSiMe (NSiMe = 4-methylpyridine-2-yloxydimethylsilyl) species are not stable under hydrogen atmosphere but are effective catalysts for the reduction of CO2 with hydrosiloxanes to silylformate under solvent-free conditions and moderate CO2 pressures and temperatures. Moreover, while using iridium(III)-DHBP half-sandwich complexes, high CO2 and H2 pressures are required to achieve the catalytic CO2 hydrogenation to methanol; Ir-NSiMe species catalyze the reduction of CO2 to methoxysilane with hydrosiloxanes under low CO2 pressure. -
Electroreduction of Carbon Dioxide by Homogeneous Iridium Catalysts
Ryoichi KanegaThe chapter delves into the electroreduction of carbon dioxide (CO2) using homogeneous iridium catalysts, highlighting their potential to address the challenges of renewable energy storage and transportation. It focuses on the production of formate, carbon monoxide, and oxalate, and discusses the development of efficient catalysts that facilitate these transformations with low overpotentials and high current densities. The text explores the mechanisms involved in these electrochemical reactions, including the role of metal hydride intermediates and the impact of ligand design on catalytic performance. Additionally, it compares the efficiency of iridium catalysts with other metal-based systems and provides insights into future research directions, such as the synthesis of methanol.AI Generated
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AbstractThe electroreduction of carbon dioxide (CO2) to chemical fuels provides not only a means to utilize CO2 but also a solution to challenges relating to the storage and transport of renewable energy. For this purpose, a range of catalysts for the electroreduction of CO2 have been studied, and recent progress in the context of tuning catalytic properties and understanding their mechanism of action has been remarkable. For example, molecular approaches allow fine-tuning of the catalyst behavior by the design of suitable ligands to suppress the overpotential for CO2 conversion. This chapter focuses on homogeneous iridium catalysts for the electroreduction of CO2, whereby the examples provided give mechanistic insight into the design of catalysts to efficiently and selectively produce electroreduced compounds from CO2 using electricity. -
Homogenous Iridium Catalysts for Biomass Conversion
Sarah Kirchhecker, Brian Spiegelberg, Johannes G. de VriesThe chapter delves into the importance of sustainable alternatives to fossil fuels, emphasizing the need for biomass conversion. It begins by introducing the use of homogeneous iridium catalysts in biomass conversion, highlighting their advantages in transforming bio-derived compounds. The chapter is divided into sections based on the substrates, focusing on sugars, bio-derived alcohols, glycerol, lignin, and fatty acids. It discusses hydrogenation, dehydrogenation, and other transformations, showcasing the versatility of iridium catalysts in these processes. The chapter also covers recent trends and innovations, making it a valuable resource for professionals in the field of catalysis and biomass conversion.AI Generated
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AbstractThe use of biomass as a sustainable feedstock for the production of chemicals has become more and more important in recent years. Homogeneous iridium catalysis offers great opportunities for the conversion of bio-derived platform molecules and even biomass components such as cellulose or lignin, due to the air, water, and acid stability of many iridium complexes. In this chapter, we review the application of iridium catalysts to the transformations of carbohydrate-derived compounds, fatty acids, and lignin. -
Iridium Nanoparticles for Hydrogenation Reactions
Luis M. Martínez-Prieto, Israel Cano, Piet W. N. M. van LeeuwenThe chapter delves into the significance of catalysis in green chemistry, focusing on the advantages and disadvantages of homogeneous and heterogeneous catalysis. It introduces metal nanoparticles (MNPs) as a promising solution that combines the benefits of both types. The primary focus is on iridium nanoparticles (Ir NPs) due to their high activity and oxidation resistance. The chapter discusses the influence of various stabilising agents, such as ligands, ionic liquids, polymers, and supports, on the hydrogenation activity of Ir NPs. It also covers recent advances in Ir NPs for hydrogenation reactions, including their use in the hydrogenation of aromatic compounds, ketones, aldehydes, and other unsaturated compounds. The chapter highlights the importance of understanding the role of stabilising agents in enhancing the stability and activity of Ir NPs, making it a valuable resource for researchers and professionals in the field of catalysis.AI Generated
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AbstractThe use of iridium nanoparticles (Ir NPs) as catalysts for hydrogenation reactions is reviewed with an emphasis on the recent advances in this area. Different types of Ir NPs are examined: NPs immobilised on supports, ligand-stabilised NPs, confined NPs, NPs stabilised by ionic liquids and polymers and NPs generated in situ without stabilising agent. A key issue is the role of the stabiliser in the catalytic process (activity, selectivity and recyclability). General trends in the use of conditions, stabilisers, additives and co-catalysts were also observed. In spite of the advances achieved in the last decade, there is still a quest for Ir NP-based catalysts with sufficient selectivity to be industrially applied in fine chemistry. -
Correction to: Chapters
Francisco J. Fernández-Alvarez, Luis A. Oro -
Correction to: Iridium Catalysts for Organic Reactions
Luis A. Oro, Carmen Claver
- Title
- Iridium Catalysts for Organic Reactions
- Editors
-
Prof. Dr. Luis A. Oro
Prof. Dr. Carmen Claver
- Copyright Year
- 2021
- Publisher
- Springer International Publishing
- Electronic ISBN
- 978-3-030-69083-0
- Print ISBN
- 978-3-030-69082-3
- DOI
- https://doi.org/10.1007/978-3-030-69083-0
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