Visible Light Photocatalyzed Redox-Neutral Organic Reactions and Synthesis of Novel Metal-Organic Frameworks

Visible Light Photocatalyzed Redox-Neutral Organic Reactions and Synthesis of Novel Metal-Organic Frameworks
Author: Basudev Sahoo
Publisher: Springer
Total Pages: 274
Release: 2016-11-25
Genre: Science
ISBN: 3319483501

This unique thesis discusses the development of conceptually novel and synthetically valuable methods that use visible light photocatalysis. Each chapter addresses a different topic in the emerging field of photocatalysis, which has become an indispensable tool for organic synthesis. Photocatalysis employs environmentally harmless and abundant visible light in the presence of a photosensitizer, and as such offers an attractive alternative to harmful UV light in photo-mediated reactions. This book introduces the novel concept of merging gold catalysis with visible light photocatalysis in a dual catalytic fashion, which demonstrates their compatibility with each other for first time and has inspired the development of various reactions. Moreover, a novel trifluoromethylation method, which combines radical addition chemistry with a polar rearrangement to synthesize valuable fluorinated compounds, is presented, since compounds featuring fluorinated functionality are the subject of increasing attention in pharmaceutical, agrochemical and material research. It also develops an external photocatalyst-free photochemical method for the synthesis of valuable indolizine heterocycles, where the product mediates its own formation. Lastly, it describes the synthesis and characterization of two novel highly porous metal-organic frameworks (MOFs). The comprehensive text is rounded out with illustrations and color figures.

Advances in Heterocyclic Chemistry

Advances in Heterocyclic Chemistry
Author:
Publisher: Academic Press
Total Pages: 437
Release: 2019-03-19
Genre: Science
ISBN: 0128174749

Advances in Heterocyclic Chemistry, Volume 129 is the definitive series in the field—one of great importance to organic chemists, polymer chemists and many biological scientists. Because biology and organic chemistry increasingly intersect, the associated nomenclature also is being used more frequently in explanations. Written by established authorities in the field from around the world, this comprehensive, updated release includes chapters on Metal-Catalyzed Direct Arylation of 1,2-Azoles, The Literature of Heterocyclic Chemistry, Part XVII, 2017, Pyrrolo-, Imidazoquinolines and Pyrroloquinazolines with a Bridgehead Nitrogen, Synthesis and Reactions of Arsole, Stibole, and Bismole, Advances in Synthesis and Chemistry of Aziridines, and more. Considered the definitive serial in the field of heterocyclic chemistry Serves as the go-to reference for organic chemists, polymer chemists and many biological scientists Provides the latest comprehensive reviews written by established authorities in the field Combines descriptive synthetic chemistry and mechanistic insight to enhance understanding of how chemistry drives the preparation and useful properties of heterocyclic compounds

Zinc Catalysis

Zinc Catalysis
Author: Stephan Enthaler
Publisher: John Wiley & Sons
Total Pages: 326
Release: 2015-04-27
Genre: Technology & Engineering
ISBN: 3527335986

Filling the gap in the market for comprehensive coverage of this hot topic, this timely book covers a wide range of organic transformations, e. g. reductions of unsaturated compounds, oxidation reactions, Friedel-Crafts reactions, hydroamination reactions, depolymerizations, transformations of carbon dioxide, oxidative coupling reactions, as well as C-C, C-N, and C-O bond formation reactions. A chapter on the application of zinc catalysts in total synthesis is also included. With its aim of stimulating further research and discussion in the field, this is a valuable reference for professionals in academia and industry wishing to learn about the latest developments.

Visible-Light Mediate Redox Processes

Visible-Light Mediate Redox Processes
Author: Spencer Paul Pitre
Publisher:
Total Pages:
Release: 2017
Genre:
ISBN:

Over the past decade, the field of photoredox catalysis has garnered increasing amounts of attention in the organic chemistry community due to its wide applicability in sustainable free radical-mediated processes. Several examples have demonstrated that under carefully optimized conditions, efficient and highly selective processes can be developed through excitation of a photosensitizer using inexpensive, readily available light sources. Furthermore, these reactions can generally be performed under milder conditions than thermal reactions, as all the energy required to overcome the reaction barrier is supplied by light. Despite all these recent advancements in the field, many of these discoveries often lack in depth investigations into the excited state kinetics and underlying mechanisms. Furthermore, the vast majority of these transformations are photocatalyzed by ruthenium and iridium polypyridyl complexes. Not only are these precious metal catalysts extremely costly, but these metals are also known to be toxic, limiting their potential use in the development of pharmaceutical protocols. Herein, we present our solutions to these shortcomings, which involve a three-prong approach in the development of novel protocols, understanding the underlying mechanisms through detailed kinetic analysis, and by the development of new tools to facilitate mechanistic investigation for practitioners who may not possess specialized photochemical equipment. In this work, we were the first to demonstrate that radicals derived from amines, commonly employed as "sacrificial" electron-donors, can also act as reducing agents in photoredox transformations. We also present examples in which Methylene Blue, an inexpensive, non-toxic organic dye, can be employed as a viable alternative to ruthenium complexes for photoredox transformations. By employing a photosensitizer with more favourable excited state kinetics for electron-transfer, we successfully demonstrated that Methylene Blue could be used to increase the efficiency of a previously developed photoredox transformation. While employing organic dyes is an excellent strategy to lowering the cost of photoredox transformations, another viable strategy is to employ heterogeneous semiconductors. Titanium dioxide is an example of a semiconductor which is often employed in photocatalytic applications due to its low cost, desirable redox properties, and high chemical stability which allows for continued use. However, titanium dioxide has seen limited use in organic synthesis due to the requirement of UV irradiation for excitation. Herein, we present a process which led to the discovery of visible light photochemistry with titanium dioxide, generated through the adsorption of indole substrates creating a new, visible light absorbing complex. Employing this strategy, we were able to promote the photocatalytic Diels-Alder reaction of indoles with electron-rich dienes, giving access to valuable tetrahydrocarbazole scaffolds. Finally, in order to facilitate the characterization of chain processes in photoredox catalysis, we have successfully developed a visible light actinometer based on the ubiquitous photocatalyst, Ru(bpy)3Cl2. This actinometer offers many advantages compared to other visible light actinometers, such as completely eliminating the need for spectral matching, as the actinometer is also the photocatalyst. This technique should provide researchers with a mechanistic tool to properly characterize chain propagation in the transformation of interest.

Design, Synthesis, Stability, and Photocatalytic Studies of Sustainable Metal-organic Frameworks

Design, Synthesis, Stability, and Photocatalytic Studies of Sustainable Metal-organic Frameworks
Author: Matthew Wade Logan
Publisher:
Total Pages: 350
Release: 2018
Genre:
ISBN:

The presented dissertation focuses on the design, synthesis, and characterization of metal-organic frameworks (MOFs) composed of earth-abundant elements the exhibit photoredox activity and studied their application as heterogeneous photocatalysts in organic synthesis and in solar-to-chemical energy conversion. In particular, the structure-property relationships of titanium-based MOFs relating the structure of the organic building unit and the photophysical and photochemical activity of the solid material is studied. The first novel family of seven MOFs isoreticular to MIL-125-NH2, includes functionalized with N-alkyl groups with increasing chain length (methyl to heptyl) and with varying connectivity (primary or secondary). The functionalized materials displayed reduced optical bandgaps correlated with the increased inductive donor ability of the alkyl substituents, enhanced excited-state lifetimes, mechanistic information towards visible light CO2 reduction, and improved water stability. The second family of titanium MOFs was prepared with a new secondary building unit and organic links of varying lengths, for which Their crystal structure was solved utilizing powder X-ray diffraction crystallography. This work provides guidelines for the next generation of photocatalyst for the conversion of solar-to-chemical energy and other organic transformations.

Visible Light Photocatalysis in Organic Chemistry

Visible Light Photocatalysis in Organic Chemistry
Author: Corey R. J. Stephenson
Publisher:
Total Pages:
Release: 2018
Genre: Chemistry, Organic
ISBN: 9781523118533

Filling the need for a ready reference that reflects the vast developments in this field, this book presents everything from fundamentals, applications, various reaction types, and technical applications. Edited by rising stars in the scientific community, the text focuses solely on visible light photocatalysis in the context of organic chemistry. This primarily entails photo-induced electron transfer and energy transfer chemistry sensitized by polypyridyl complexes, yet also includes the use of organic dyes and heterogeneous catalysts. A valuable resource to the synthetic organic community, polymer and medicinal chemists, as well as industry professionals.

Organic Redox Systems

Organic Redox Systems
Author: Tohru Nishinaga
Publisher: John Wiley & Sons
Total Pages: 627
Release: 2015-11-25
Genre: Science
ISBN: 1118858859

Providing a thorough overview of leading research from internationally-recognized contributing authors, this book describes methods for the preparation and application of redox systems for organic electronic materials like transistors, photovoltaics, and batteries. Covers bond formation and cleavage, supramolecular systems, molecular design, and synthesis and properties Addresses preparative methods, unique structural features, physical properties, and material applications of redox active p-conjugated systems Offers a useful guide for both academic and industrial chemists involved with organic electronic materials Focuses on the transition-metal-free redox systems composed of organic and organo main group compounds

Introduction to Reticular Chemistry

Introduction to Reticular Chemistry
Author: Omar M. Yaghi
Publisher: John Wiley & Sons
Total Pages: 684
Release: 2019-03-22
Genre: Science
ISBN: 3527821104

A concise introduction to the chemistry and design principles behind important metal-organic frameworks and related porous materials Reticular chemistry has been applied to synthesize new classes of porous materials that are successfully used for myraid applications in areas such as gas separation, catalysis, energy, and electronics. Introduction to Reticular Chemistry gives an unique overview of the principles of the chemistry behind metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and zeolitic imidazolate frameworks (ZIFs). Written by one of the pioneers in the field, this book covers all important aspects of reticular chemistry, including design and synthesis, properties and characterization, as well as current and future applications Designed to be an accessible resource, the book is written in an easy-to-understand style. It includes an extensive bibliography, and offers figures and videos of crystal structures that are available as an electronic supplement. Introduction to Reticular Chemistry: -Describes the underlying principles and design elements for the synthesis of important metal-organic frameworks (MOFs) and related materials -Discusses both real-life and future applications in various fields, such as clean energy and water adsorption -Offers all graphic material on a companion website -Provides first-hand knowledge by Omar Yaghi, one of the pioneers in the field, and his team. Aimed at graduate students in chemistry, structural chemists, inorganic chemists, organic chemists, catalytic chemists, and others, Introduction to Reticular Chemistry is a groundbreaking book that explores the chemistry principles and applications of MOFs, COFs, and ZIFs.

Applied Organic Chemistry

Applied Organic Chemistry
Author: Surya K. De
Publisher: John Wiley & Sons
Total Pages: 856
Release: 2021-03-08
Genre: Science
ISBN: 3527347852

An indispensable guide for all synthetic chemists who want to learn about the most relevant reactions and reagents employed to synthesize important heterocycles and drugs! The synthesis of natural products, bioactive compounds, pharmaceuticals, and drugs is of fundamental interest in modern organic chemistry. New reagents and reaction methods towards these molecules are being constantly developed. By understanding the mechanisms involved and scope and limitations of each reaction applied, organic chemists can further improve existing reaction protocols and develop novel efficient synthetic routes towards frequently used drugs, such as Aspirin or Penicillin. Applied Organic Chemistry provides a summary of important (name) reactions and reagents applied in modern organic chemistry and drug synthesis. It covers rearrangement, condensation, olefination, metathesis, aromatic electrophilic substitutions, Pd-catalyzed C-C bond forming reactions, multi-component reactions, as well as oxidations and reductions. Each chapter is clearly structured, providing valuable information on reaction details, step-by-step mechanism, experimental procedures, applications, and (patent) references. By providing mechanistic information and representative experimental procedures, this book is an indispensable guide for researchers and professionals in organic chemistry, natural product synthesis, pharmaceutical, and medicinal chemistry, as well as post-graduates preparing themselves for a job in the pharmaceutical industry. Hot Topic: Reviews important classes of organic reactions (incl. name reactions) and reagents in medicinal chemistry. Useful: Provides information on reaction details, common reagents, and functional group transformations used to synthesize natural products, bioactive compounds, drugs, and pharmaceuticals, e.g. Aspirin, Penicillin. Unique: For every reaction the mechanism is explained step by step, and representative experimental procedures are given, unlike most books in this area. User-friendly: Chapters are clearly structured making it easy for the reader to compare different reactions. Applied Organic Chemistry is an indispensable guide for researchers and professionals in organic chemistry, natural product synthesis, pharmaceutical, and medicinal chemistry, as well as post-graduates preparing themselves for a job in the pharmaceutical industry.

Metal-Organic Framework Nanocomposites

Metal-Organic Framework Nanocomposites
Author: Anish Khan
Publisher: CRC Press
Total Pages: 339
Release: 2020-11-24
Genre: Technology & Engineering
ISBN: 1000244865

Metal-Organic Framework Nanocomposites: From Design to Application assembles the latest advances in MOF nanocomposites, emphasizing their design, characterization, manufacturing, and application and offering a wide-ranging view of these materials with exceptional physical and chemical properties. FEATURES Discusses various types of MOF materials, such as polyaniline MOF nanocomposites, magnetic MOF nanocomposites, and carbon nanotube-based MOF nanocomposites Includes chapters on the usage of these materials in pollutant removal, electrochemical devices, photocatalysts, biomedical applications, and other applications Covers different aspects of composite fabrication from energy storage and catalysts, including preparation, design, and characterization techniques Emphasizes the latest technology in the field of manufacturing and design Aimed at researchers, academics, and advanced students in materials science and engineering, this book offers a comprehensive overview and analysis of these extraordinary materials.