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(Cont.) Carbon dioxide also inserts into the Cu-Si bond of a copper silyl complex. The resulting complex evolves CO to give a copper siloxide complex. Mesitaldehyde inserts cleanly and selectively into the Cu-B bond of (NHC)CuB(pin), to form a B-O and a copper-carbon bond. This complex reacts with bis(pinacolato)diboron to regenerate (NHC)CuB(pin) and produce an aldehyde diboration product, in which a diboron reagent has been added across the C=O bond of mesitaldehyde. A copper boryl complex with a smaller NHC supporting ligand proved to be a much more effective diboration catalyst and a wide range of aldehydes react cleanly with bis(pinacolato)diboron. The insertion of alkenes into an (NHC)copper(I) boryl affords isolable -boroalkyl complexes in high yields; competition experiments using substituted styrenes show that electron-donating substituents slow the reaction. Although the insertion products are stable at ambient temperature, a P-hydride elimination/reinsertion sequence affords a rearranged a-boroalkyl complex on heating.
In less than 20 years N-heterocyclic carbenes (NHCs) have become well-established ancillary ligands for the preparation of transition metal-based catalysts. This is mainly due to the fact that NHCs tend to bind strongly to metal centres, avoiding the need of excess ligand in catalytic reactions. Also, NHC‒metal complexes are often insensitive to air and moisture, and have proven remarkably resistant to oxidation. This book showcases the wide variety of applications of NHCs in different chemistry fields beyond being simple phosphine mimics. This second edition has been updated throughout, and now includes a new chapter on NHC‒main group element complexes. It covers the synthesis of NHC ligands and their corresponding metal complexes, as well as their bonding and stereoelectronic properties and applications in catalysis. This is complemented by related topics such as organocatalysis and biologically active complexes. Written for organic and inorganic chemists, this book is ideal for postgraduates, researchers and industrialists.
N-heterocyclic carbenes (NHCs) have found increasing use as reagents for a range of organic transformations and in asymmetric organocatalysis. The performance of these molecules can be improved and tuned by functionalisation. Functionalised carbenes can anchor free carbenes to the metal site, introduce hemilability, provide a means to immobilise transition metal carbene catalysts, introduce chirality, provide a chelate ligand or bridge two metal centres. NHC can be attached to carbohydrates and campher, derived from amino acids and purines, they can be used as organocatalysts mimicking vitamin B1 or as weak “solvent” donors in lanthanide chemistry. Functionalised N-Heterocyclic Carbene Complexes describes major trends in functionalised NHC ligands, aiming to assist readers in their attempts to develop and apply their own functionalised carbenes. After an introduction to the chemistry and behaviour of NHC, the book gives a detailed description of functionalised carbenes and their complexes according to a range of functional groups, each with a discussion of the synthetic route, structure, stability and performance. Functionalised N-Heterocyclic Carbene Complexes is an essential guide to fine-tuning this important class of compounds for practitioners, researchers and advanced students working in synthetic organometallic and organic chemistry and catalysis.
This comprehensive reference and handbook covers in depth all major aspects of the use of N-heterocyclic carbene-complexes in organic synthesis: from the theoretical background to characterization, and from cross-coupling reactions to olefin metathesis. Edited by a leader and experienced scientist in the field of homogeneous catalysis and use of NHCs, this is an essential tool for every academic and industrial synthetic chemist.
Exploring the importance of Richard F. Heck’s carbon coupling reaction, this book highlights the subject of the 2010 Nobel Prize in Chemistry for palladium-catalyzed cross couplings in organic synthesis, and includes a foreword from Nobel Prize winner Richard F. Heck. The Mizoroki-Heck reaction is a palladium-catalyzed carbon–carbon bond forming process which is widely used in organic and organometallic synthesis. It has seen increasing use in the past decade as chemists look for strategies enabling the controlled construction of complex carbon skeletons. The Mizoroki-Heck Reaction is the first dedicated volume on this important reaction, including topics on: mechanisms of the Mizoroki-Heck reaction intermolecular Mizoroki-Heck reactions focus on regioselectivity and product outcome in organic synthesis waste-minimized Mizoroki-Heck reactions intramolecular Mizoroki-Heck reactions formation of heterocycles chelation-controlled Mizoroki-Heck reactions the Mizoroki-Heck reaction in domino processes oxidative heck-type reactions (Fujiwara-Moritani reactions) Mizoroki-Heck reactions with metals other than palladium ligand design for intermolecular asymmetric Mizoroki-Heck reactions intramolecular enantioselective Mizoroki-Heck reactions desymmetrizing Mizoroki-Heck reactions applications in combinatorial and solid phase syntheses, and the development of modern solvent systems and reaction techniques the asymmetric intramolecular Mizoroki-Heck reaction in natural product total synthesis Several chapters are devoted to asymmetric Heck reactions with particular focus on the construction of otherwise difficult-to-obtain sterically congested tertiary and quaternary carbons. Industrial and academic applications are highlighted in the final section. The Mizoroki-Heck Reaction will find a place on the bookshelves of any organic or organometallic chemist. “I am convinced that this book will rapidly become the most important reference text for research chemists in academia and industry who seek orientation in the rapidly growing and – for the layman – confusing field described as the “’Mizoroki–Heck reaction’.” (Synthesis, March 2010)
This first handbook to focus solely on the application of N-heterocyclic carbenes in synthesis covers metathesis, organocatalysis, oxidation and asymmetric reactions, along with experimental procedures. Written by leading international experts this is a valuable and practical source for every organic chemist.
The objective of this research is to create unique and highly functional N-heterocyclic carbene complexes that provide maximum catalytic features in close proximity to the metal centers. The N-heterocyclic carbenes created over the past 20 years have generally consisted of imidazole moieties substituted at both nitrogen atoms with alkyl and aryl substitutents. These typical N-heterocylic carbenes have presented many highly stable and tunable complexes used in catalysis, however, some beneficial features would be imparted on these N-heterocyclic carbenes if one of the alkyl and aryl substituted sites were allowed to remain un-substituted. These unique atypical protic N-heterocyclic carbenes allow for acid base chemistry to occur in close proximity to the metal center while simultaneously providing the tunable, highly sigma-donating features of a typical N-heterocyclic carbene. The research presented in this thesis explores the synthetic approach to atypical protic N-heterocyclic carbene ligand precursors as well as their complexation and subsequent catalytic capabilities. Two ligand precursor families were created: one consisting of an iodobenzene moiety attached to a tert-butyl imidazole group, and one in which a pyridine ring moiety is attached to a tert-butyl imidazole group. The iodobenzene group yielded two ligand precursors, 2a and 2b, both containing methylene spacers between the auxiliary moiety and tert-butyl groups. The pyridine-containing family consisted of 3a, where the tert-butyl imidazole was directly attached to the pyridine ring, and 3c, where the tert-butyl imidazole was attached to the ring by a methylene spacer. Attempts to complex the first ligand precursor family 2a and 2b were unsuccessful and lead to the synthesis of the pyridine analogues 3a and 3c which were successfully complexed to both iridium and rhodium metal centers yielding: Ir-Phos- 3a, Ir-Phos-3c, Ir-S0-3a, Ir-S1-3c, Rh-S0-3a, and Rh-S1-3c. Catalytic studies carried out with the six complexes above consisted of the oxidation of alcohols to their corresponding ketones. These catalytic tests revealed a higher degree of successful turnover with the 3c containing complexes. Crystallographic data suggests that bond angles and bond distances found in 3c containing complexes give inherent advantages to the 3c containing complexes due to the flex allowed by the methylene spacer. Additionally, catalytic comparisons of methylated analogues of 3c with the atypical protic 3c complexes showed a decrease in catalytic activity suggesting that the presences of the un-substituted nitrogen in close proximity to the metal center yields the predicted benefit of using atypical protic N-heterocyclic carbenes.
The book ‘Organic Synthesis - A Nascent Relook’ is a compendium of the recent progress in all aspects of organic chemistry including bioorganic chemistry, organo-metallic chemistry, asymmetric synthesis, heterocyclic chemistry, natural product chemistry, catalytic, green chemistry and medicinal chemistry, polymer chemistry, as well as analytical methods in organic chemistry. The book presents the latest developments in these fields. The chapters are written by chosen experts who are internationally known for their eminent research contributions. Organic synthesis is the complete chemical synthesis of a target molecule. In this book, special emphasis is given to the synthesis of various bioactive heterocycles. Careful selection of various topics in this book will serve the rightful purpose for the chemistry community and the industrial houses at all levels.
The field of N-heterocyclic carbenes, whether in transition-metal catalysis or organocatalysis, is rapidly evolving towards applications, but is also still very active on the catalyst development front. Significant advances have been made over the past two decades and the development of these reactions has dramatically improved the efficiency of organic synthesis. N-Heterocyclic carbene based catalysts are now widely applied in the area of synthesis of both natural products and therapeutic agents. Science of Synthesis: N-Heterocyclic Carbenes in Catalytic Organic Synthesis presents the most commonly used and significant metal- or non-metal-catalyzed reactions for modern organic synthesis. The basic principles and current state-of-the-art of the methods are covered. Scope, limitations, and mechanism of these reactions are discussed and key experimental procedures are included. Typical examples of target synthesis are often provided to show the utility and inspire further applications.