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Chapter 1. The Stereochemistry of C-C Bond Formation via Metal Enolates. Alkylation and Heteroatom Introduction (Y. Yamamoto and N. Sasaki). Stereochemistry of alkylation of acyclic systems. Stereochemistry of alkylation of cyclic systems. Formation of enolates, mechanism of alylation, and regioselectivity. Other metal enolates including transition metals. Asymmetric alkylation. Introduction of heteroatoms and proton at the &agr;-position. Application to natural products synthesis. Concluding remarks. References. Chapter 2. Transition-Metal Complexes of N2, CO2, and Similar Small Molecules. Ab-Initio MO Studies of their Stereochemistry and Coordinate Bonding Nature (S. Sakaki). Introduction. Brief outline of computations. General survey of coordinate bond nature. Transition-metal CO2 complexes. Structures and bonding nature of transition-metal dinitrogen complexes. Concluding remarks. References. Chapter 3. Electrochemistry of mononuclear copper complexes. Structural reorganizations accompanying redox changes (P. Zanello). Introduction. Oxygen donor ligands. Sulfur donor ligands. Nitrogen donor ligands. Mixed oxygen-sulfur ligands. Mixed oxygen-nitrogen ligands. Mixed sulfur-nitrogen ligands. Appendix. Conclusions. Abbreviations for Solvents. Subject index.
The authors of this fourth volume in the series have reviewed the making and breaking of chemical bonds in a sophisticated manner. In particular, new pressures brought about by environmental concerns, larger demands for the medical and pharmaceutical sectors and economics of the market place are forcing us into demanding greater stereochemical control and better product yields for chemical reactions capable of producing useful products. The chapters are written by leading experts in this area and give excellent overviews of the strengths and weaknesses of the various methodologies.
In Chapter 1 newer discoveries in such tried and true methods of C-C bond formation as alkylations and aldol reactions of metal enolates are reviewed. The author of Chapter 2 discusses the ability of ab-initio methods to justify the results of empirical observations in the field of transition metal derivatives of small molecules such as N2, CO2 and similar small molecules. Having established the strengths and weaknesses of the various approaches to such theoretical calculations, a more interesting approach to these methods is pursued, namely, their ability to predict, in those areas in which they are particularly strong and reliable, chemical and stereochemical events and/or results in advance of experiments, later carried out in the laboratory. Finally, Chapter 3 reviews the stereochemical results of electron transfer reactions in mononuclear copper compounds.
- © Elsevier Science 1990
- 12th September 1990
- Elsevier Science
- eBook ISBN:
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