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This book contains an overview of complex formation by macrocyclic ligand systems. The study of macrocyclic chemistry represents a major area of activity which impinges on a range of other areas in both chemistry and biochemistry. The field has characteristically yielded many interesting and unusual compounds. The text discusses the structures and properties of macrocyclic compounds; the synthesis of macrocycles; polyether crown and related systems; metal-ion and molecular recognition (host-guest chemistry); as well as kinetic, thermodynamic and electrochemical aspects of a range of macrocyclic systems. A discussion of the different categories of naturally occurring macrocycles is also included. Specialist and non-specialist alike will find this a useful text. Apart from serving as a convenient reference for established workers in the field, it should also prove useful to new graduate students as well as to researchers from other areas who seek a general introduction to the subject. The topics discussed also provide a suitable basis for a senior undergraduate or graduate course in macrocyclic chemistry and inorganic complexes.
30 years after its discovery as an antitumor agent, cisplatin represents today one of the most successful drugs in chemotherapy. This book is intended to reminisce this event, to take inventory, and to point out new lines of development in this field. Divided in 6 sections and 22 chapters, the book provides an up-to-date account on topics such as - the chemistry and biochemistry of cisplatin, - the clinical status of Pt anticancer drugs, - the impact of cisplatin on inorganic and coordination chemistry, - new developments in drug design, testing and delivery. It also includes a chapter describing the historical development of the discovery of cisplatin. The ultimate question - How does cisplatin kill a cell? - is yet to be answered, but there are now new links suggesting how Pt binding to DNA may trigger a cascade of cellular reactions that eventually result in apoptosis. p53 and a series of damage recognition proteins of the HMG-domain family appear to be involved. The book addresses the problem of mutagenicity of Pt drugs and raises the question of the possible relevance of the minor DNA adducts, e.g. of interstrand cross-links, and the possible use of trans-(NH3)2Pt(II)-modified oligonucleotides in antisense and antigene strategies. Our present understanding of reactions of cisplatin with DNA is based upon numerous model studies (from isolated model nucleobases to short DNA fragments) and application of a large body of spectroscopic and other physico-chemical techniques. Thanks to these efforts there is presently no other metal ion whose reactions with nucleic acids are better understood than Pt. In a series of chapters, basic studies on the interactions of Pt electrophiles with nucleobases, oligonucleotides, DNA, amino acids, peptides and proteins are reported, which use, among others, sophisticated NMR techniques or X-ray crystallography, to get remarkable understanding of details on such reactions. Reactivity of cisplatin, once bound to DNA and formerly believed to be inert enough to stay, is an emerging phenomenon. It has (not yet) widely been studied but is potentially extremely important. Medicinal bioinorganic chemistry - the role of metal compounds in medicine - has received an enormous boost from cisplatin, and so has bioinorganic chemistry as a whole. There is hardly a better example than cisplatin to demonstrate what bioinorganic chemistry is all about: The marriage between classic inorganic (coordination) chemistry and the other life sciences - medicine, pharmacy, biology, biochemistry. Cisplatin has left its mark also on areas that are generally considered largely inorganic. The subject of mixed-valance Pt compounds is an example: From the sleeping beauty it made its way to the headlines of scientific journals, thanks to a class of novel Pt antitumor agents, the so-called "platinum pyrimidine blues". In the aftermath diplatinum (III) compounds were recognized and studies in large numbers, and now an organometalic chemistry of these diplatinum (III) species is beginning to emerge. The final section of the book is concerned with new developments such as novel di- and trinuclear Pt(II) drugs with DNA binding properties different from those of cisplatin, with orally active Pt(IV) drugs which are presently in clinical studies, and with attempts to modify combinatorial chemistry in such a way that it may become applicable to fast screening of Pt antitumor drugs. The potential of including computational methods in solving questions of Pt-DNA interactions is critically dealt with in the concluding chapter.
"Cross-Coupling Reactions: An Overview opens with an overview of the fundamentals and applications of the young and fast developing area of transition metal catalyzed/mediated oxidative (dehydrogenative) C-H/C-H coupling reactions between two (hetero)arenes. Continuing, the authors highlight the recent advances regarding the ligand supported transition metal-catalyzed domino (cascade) or one-pot syntheses of various heterocycles involving cross-coupling reactions. The recent advances in Cu catalyzed tandem reactions for heterocycle synthesis are also addressed. Cu metal chemistry has garnered attention as a potential alternative to precious transition metals, being cheaper, more sustainable and more easily available. A comprehensive account of research on green chemical routes is provided, involving various palladium metal-based catalysts utilized in facilitating cross-coupling reaction in aqueous media. Reported decarboxylative cross-coupling reactions are discussed along with suitable examples, focusing on their mechanism of action"--
The synthesis of macrocycles is an art in itself. Template-controlled synthesis provides elegant access to fascinating macrocyclic structures. Polyazamacrocycles, crown ethers, cryptands, rotaxanes, knots -- the range of macrocyclic compounds is as broad as their potential application as molecular switches, in ion exchange, electron transfer or catalysis. This book provides authoritative information on all aspects of template-controlled macrocyclizations. It covers in depth the current state of research on template processes - novel synthetic techniques and mechanistic approaches. The critical discussion of the diverse synthetic routes includes the detailed characterization of the broad variety of macrocyclic products. References to applications of macrocyclic compounds and over 1,500 citations make this handbook an indispensable tool for chemists in academia and industry. Researchers in organic and supramolecular chemistry, biotechnology, and inorganic chemistry will find inspiration for the design, synthesis, and myriad uses of new synthetic macrocycles.