Perspectives of Hydrosilylation Reactions
- 2023
- Book
- Editors
- Bogdan Marciniec
- Hieronim Maciejewski
- Book Series
- Topics in Organometallic Chemistry
- Publisher
- Springer Nature Switzerland
About this book
This volume describes the latest advances and perspectives in hydrosilylation, with a focus on new organometallic catalysts and their mechanistic aspects. Hydrosilylation is the reaction of ≡SiH with carbon-carbon, carbon-heteroatom or heteroatom-heteroatom bonds and is the most fundamental and elegant method for laboratory and industrial synthesis of organosilicon molecular and macromolecular compounds. Yet these reactions do require a catalyst, for which initially homogeneous noble metal catalyst, mainly platinum, rhodium, iridium or ruthenium were used. However the high prices, metallic residues of these valuable catalysts as well as issues with product purification, did increase the interest in developing new catalysts. Noteworthy in this regard are the recently developed hydrosilylation reactions using catalysts based on earth-abundant transition metals (for example Mn, Fe, Co, Ni) and heterogeneous catalysts presented here.
This volume of Topics in Organometallic Chemistry is written for scientists interested in silicon chemistry and its catalytic aspects, but can also be used as valuable handbook for postgraduate and advanced undergraduate students working with organometallic chemistry, catalysis as well as synthesis of fine chemicals.
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Table of Contents
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Frontmatter
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Silicometallics vs. Organometallics and Catalysis: General Guidelines
Bogdan MarciniecThe chapter delves into the significance of organometallic and silicometallic chemistry, particularly the role of silicon derivatives in hydrosilylation processes. It discusses the formation of TM–Si bonds and their crucial role in mechanistic implications of catalytic reactions. The text highlights recent advances in hydrosilylation catalysis, including the use of non-precious metal catalysts and the development of heterogeneous catalysts. It also explores the potential of hydrosilylation in the synthesis of fine chemicals and precursors of new materials, emphasizing the importance of precise mechanistic studies and sustainable development.AI Generated
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AbstractGreat progress in the research on hydrosilylation processes, mainly those based on catalysis by TM complexes, achieved over the last 70 years, has inspired the writing of this book. It consists of 8 chapters and is concentrated not only on the most attractive publications and excellent reviews from the last decade, but above all on the presentation of perspectives of research in this area in the next few decades. The aim of Chapter “Silicometallics vs. Organometallics and Catalysis: General Guidelines” is to formulate a vision for such perspective development of this field, including new mechanistic aspects of TM-catalyzed hydrosilylation involving intermediates containing transition metal–silicon (TM–Si), i.e., silicometallics and TM–H bonds leading to selective synthesis of silicon-containing products—fine chemicals and precursors of materials. However, the guideline idea is to highlight a crucial role of TM–Si intermediates, using homogeneous and heterogeneous systems, in application of hydrosilylation reactions. The most industrially important processes for the synthesis of organosilicon molecular and polymeric compounds will lead to development of advanced technologies and, finally, to their transfer to innovative firms for production of new and hybrid materials of expected and unexpected properties. -
Recent Advances of Group 10 Transition Metal Hydrosilylation Catalysts
Shigeru ShimadaThe chapter delves into the recent advancements of Group 10 transition metal hydrosilylation catalysts, particularly focusing on homogeneous and heterogeneous Pt catalysts. It begins with an overview of the historical significance of Karstedt’s catalyst, which remains the most widely used hydrosilylation catalyst due to its high efficiency. The chapter then explores the development of non-precious metal catalysts, such as Ni and Pd, which have gained significant attention due to their potential to replace Pt catalysts in practical applications. It discusses the various types of Pt catalysts, including NHC-Pt complexes and their improved stability and selectivity. The chapter also highlights the advancements in heterogeneous Pt catalysts, such as Pt NPs supported on various materials, and their applications in hydrosilylation reactions. Additionally, it covers the development of single atom Pt catalysts and their unique properties. The chapter concludes with a discussion on the future directions of hydrosilylation catalysts, emphasizing the need for more efficient and stable catalysts.AI Generated
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AbstractThis chapter summarizes recent advances of group 10 transition metal hydrosilylation catalysts from 2015 onward. Since the discovery of Speier’s catalyst in 1957, homogeneous Pt catalysts have been mainly used for the hydrosilylation reaction of C-C multiple bonds. Although research on homogeneous Pt hydrosilylation catalysts has still been intensive, recent trends of research that meet the demands for sustainable development significantly increased the research on heterogeneous and non-precious metal hydrosilylation catalysts including Ni catalysts. Although Pd catalysts are very popular in organic transformation, its usefulness in hydrosilylation reaction is relatively limited, except for several special cases such as asymmetric hydrosilylation. -
State of the Art in Rhodium- and Iridium-Catalyzed Hydrosilylation Reactions
Manuel Iglesias, Francisco J. Fernández-Alvarez, Luis A. OroThis chapter offers a detailed review of the state-of-the-art in rhodium and iridium-catalyzed hydrosilylation reactions, with a particular emphasis on developments since 2009. It covers a wide range of substrates, including alkynes, alkenes, ketones, CO2, amides, imines, and nitriles. The chapter highlights the significant untapped potential of rhodium and iridium in these reactions, despite their long history of use. It delves into the selectivity issues and recent advancements in catalyst design, such as the use of N-heterocyclic carbenes and bimetallic complexes. Additionally, the chapter discusses the functionalization of ligands for catalyst immobilization and the development of hybrid systems with improved recyclability. The comprehensive overview makes this chapter an essential resource for those interested in the latest developments in hydrosilylation catalysis.AI Generated
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AbstractThis chapter reviews the state of the art of rhodium- and iridium-catalyzed hydrosilylation reactions, demonstrating the utility of rhodium and iridium catalysts for organic synthesis. Nowadays, this field has solid and proven mechanistic foundations that allow the design, development, and optimization of new catalytic systems. As this chemistry will undoubtedly continue to make relevant progress, it deserves constant attention. -
Recent Development of Cobalt-Catalyzed Hydrosilylation Reactions: New Catalysts, Mechanistic Understandings, and Future Trends
Dongyang Wang, Liang DengThe chapter 'Recent Development of Cobalt-Catalyzed Hydrosilylation Reactions: New Catalysts, Mechanistic Understandings, and Future Trends' offers a comprehensive exploration of recent advancements in cobalt-catalyzed hydrosilylation reactions. It delves into the unique characteristics of cobalt as a first-row late transition metal and its application in hydrosilylation reactions. The chapter is organized by the type of unsaturated organic substrates, focusing on alkenes and alkynes. It discusses the development of various cobalt catalysts, including those with isocyanide, NHC, nitrogen, and phosphine ligands, and their impact on selectivity and reactivity. The chapter also highlights the challenges and future trends in the field, such as the development of enantioselective hydrosilylation reactions and the synthesis of chiral hydrosilanes. Additionally, it covers the hydrosilylation of allenes and enynes, as well as the double hydrosilylation of alkynes, providing a thorough overview of the latest research in this dynamic area of catalysis.AI Generated
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AbstractThis chapter presents a comprehensive summary of cobalt-catalyzed hydrosilylation of alkenes and alkynes from 2016 to 2023 with the objective of providing readers with the status of this field. Various well-defined cobalt complexes bearing structurally diverse nitrogen-based ligands, phosphines, NHCs, and isocyanides are developed. Their catalytic application in the hydrosilylation reactions of alkenes and alkynes led to the development of new catalytic systems with different chemo-, regio-, and stereoselectivity. Different substrate activation and chemical bond construction modes are proposed based on mechanistic study, which contributes to a better understanding of the chemistry of cobalt-catalyzed hydrosilylation reaction. In addition, the problems and perspectives in this field are also presented. -
Iron and Manganese Catalyzed Hydrosilylation Reactions
Thaipparambil Aneeja, Pulluparambil Xavier Thresia Rinu, Gopinathan AnilkumarThe chapter delves into the significant role of hydrosilylation reactions in organic transformations, emphasizing the shift from noble metals to earth-abundant first-row transition metals like iron and manganese. It summarizes recent developments from 2015 to 2023, focusing on the hydrosilylation of carbonyl compounds, alkenes, alkynes, and imines. The chapter highlights the high catalytic efficiency, low toxicity, and excellent functional group tolerance of iron and manganese-based catalysts. Notable advancements include the development of iron piano stool complexes, iron hydrido complexes, and manganese pincer complexes for hydrosilylation reactions. The chapter also discusses the use of visible light in manganese-catalyzed alkyne hydrosilylation and the hydrosilylation of carbon dioxide. Throughout, the chapter emphasizes the importance of these earth-abundant metals in sustainable and green chemistry.AI Generated
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AbstractHydrosilylation reaction has emerged as an important strategy for the preparation of silicone polymers and functionalized silanes. Most of the reports on hydrosilylation reactions rely on rare, toxic, and expensive noble metals such as Pd, Pt, Ir, Rh, etc. However, in view of the growing environmental concerns, the development of more ecofriendly protocols using less expensive transition metals like Fe, Co, Mn, Ni, etc. is highly demanding. Recently, transition metals are widely exploited as catalysts for hydrosilylation reactions. Considering the tremendous interest in hydrosilylation reactions and transition metal catalysis, in this chapter we summarize the recent advances in iron and manganese catalyzed hydrosilylation reactions. -
Catalysis of Hydrosilylation Processes with the Participation of Ionic Liquids
Hieronim Maciejewski, Magdalena Jankowska-Wajda, Izabela DąbekThe chapter discusses the significance of hydrosilylation processes in the silicone industry, focusing on the catalytic systems used to facilitate these reactions. Traditional catalysts, such as platinum and rhodium complexes, are expensive and pose environmental concerns. The chapter explores the use of ionic liquids as an alternative, highlighting their advantages in terms of solubility, stability, and recyclability. It delves into the application of ionic liquids as solvents and immobilizing agents, showcasing their effectiveness in two-phase systems. The chapter also covers the development of heterogeneous catalysts with ionic liquids, such as SILP and SCILL systems, which offer improved catalyst isolation and reusability. Additionally, it introduces the concept of ionic liquid-based metal complexes and anionic metal complexes, providing insights into their synthesis and catalytic activities. The chapter concludes by discussing the potential of continuous processes using ionic liquids, emphasizing their role in enhancing the efficiency and sustainability of hydrosilylation reactions.AI Generated
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AbstractHydrosilylation processes are still most often catalyzed using homogeneous complexes of transition metals (mainly platinum and rhodium). However, due to economic (high prices of precious metals), ecological (unacceptable presence of heavy metals in products), and technological (difficulties in removing catalysts from products and trying to recycle them) other catalytic systems are still being sought. In addition to the new earth-abundant TM-based catalysts (which are still not as effective as platinum complexes), heterogenized catalysts are increasingly being used. This chapter presents examples of such catalysts, which were obtained with the use of ionic liquids as a platform for the heterogenization of highly active Rh and Pt complexes. Ionic liquids (ILs) in these catalytic systems play different roles, as (i) a solvent dissolving the catalyst and an immobilizing agent (biphasic system), (ii) an immobilizing layer with a solid support (supported ionic liquid phase—SILP and solid catalysts with ILs layer SCILL), (iii) ligand in metal complexes, or (iv) complexes (halometallate ionic liquid). All of the above catalytic systems show high activity in hydrosilylation processes and also enable easy isolation and multiple use. -
Hydrosilylation Catalysis for One-Pot Synthesis
Ken MotokuraThis chapter delves into the advantages and applications of hydrosilylation catalysis in one-pot synthesis, a method that combines multiple reactions in a single reactor. It discusses the unique reactivity of silicon atoms, which confers advantages for one-pot synthesis, and classifies recent examples into three groups: one-pot synthesis with Si as a leaving group, Si as an intersection, and hydrosilylation followed by functionalization. The chapter explores various reaction conditions, catalysts, and proposed reaction mechanisms, emphasizing the economic and time-efficient benefits of one-pot synthesis. It also highlights the versatility of hydrosilylation in producing various organic compounds, such as substituted alkenes, formamides, tetralin derivatives, and oligosiloxanes. The chapter concludes by emphasizing the importance of highly active and selective catalysis in rapid and complex molecule synthesis through one-pot procedures.AI Generated
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AbstractOne-pot synthesis, including the hydrosilylation of alkenes, alkynes, carbonyl compounds, CO2, and other molecules, enables the facile synthesis of final products with high efficiency. This chapter describes recent advances in three types of one-pot syntheses triggered by hydrosilylation: (i) one-pot synthesis with Si as a leaving group, (ii) one-pot synthesis with Si as an intersection, and (iii) other successive reactions, including hydrosilylation and functionalization reactions. Synthetic utilities such as the substrate scope and homogeneous/heterogeneous catalysis with mechanistic aspects are also discussed. -
Hydrosilylation of Carbon–Carbon Multiple Bonds in Organic Synthesis
Maciej Zaranek, Piotr PawlućThis chapter delves into the pivotal role of hydrosilylation in organic synthesis, emphasizing its direct and adaptable method for introducing silyl groups into unsaturated molecules. It covers the historical significance of organosilicon reagents, particularly the Tamao–Fleming procedure and the Hiyama–Denmark cross-coupling. The text also explores the burgeoning interest in sequential processes involving hydrosilylation, such as the synthesis of intricate molecules from simple substrates. Furthermore, it discusses the development of platinum-free catalysis methods and the application of first-row transition metal catalysts in regio- and stereoselective hydrosilylation. The chapter highlights the versatility of these methods in generating valuable intermediates for various organic reactions, including the synthesis of enantioenriched secondary alcohols and hydroxy-substituted (E,E)-1,3-dienes. Additionally, it covers the advancements in asymmetric hydrosilylation of alkenes and the potential of transition metal-catalyzed sequential double hydrofunctionalization of alkynes. The text concludes by emphasizing the potential of these methods in the synthesis of natural products and other complex organic compounds, making it a valuable resource for specialists in organic chemistry.AI Generated
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AbstractHydrosilylation of alkenes and alkynes is the most fundamental and elegant method for laboratory and industrial synthesis of organosilicon compounds, which can be directly used in organic synthesis. The aim of this chapter is to present a concise overview of the most attractive results of the application of regio- and stereoselective hydrosilylation of alkenes and alkynes published mainly in the last decade. The chapter consists of sections discussing sequential reactions involving hydrosilylation of functional alkenes and alkynes as the initial step followed by desilylation (oxidation, cross-coupling), double hydrofunctionalization of alkynes including hydrosilylation, and asymmetric hydrosilylation of prochiral alkenes. In our chapter, we highlight the applications of new catalysts based on first-row transition metal complexes in consecutive (also one-pot) hydrosilylation/desilylation reactions. Special attention has been paid to enantioselective hydrosilylation of olefins, which has been experiencing a renaissance in recent years and is an extremely attractive method in the synthesis of chiral silanes, alcohols, and their derivatives.
- Title
- Perspectives of Hydrosilylation Reactions
- Editors
-
Bogdan Marciniec
Hieronim Maciejewski
- Copyright Year
- 2023
- Publisher
- Springer Nature Switzerland
- Electronic ISBN
- 978-3-031-45960-3
- Print ISBN
- 978-3-031-45959-7
- DOI
- https://doi.org/10.1007/978-3-031-45960-3
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