The demand for selective organic reactions is growing more acute everyday. Indeed, greater product selectivity has an important impact on energy and resource utilization, in terms of reduced process energy requirements for product separation and purification, in terms of low-value by-products, and in terms of environmental acceptance and compatibility. Moreover, more and more chemicals, especially pharmaceuticals, have to be sold in an optically active form. The search for selectivity constitutes a tremendous challenge for the chemists. In the last two decades, homogeneous transition metal based catalysis has emerged as one of the most promising tools for obtaining selectivity. In connection with developments in this area, this book contains updated and expanded versions of most of the lectures presented at a Cornett course held in Trieste (Italy) in 1989 and sponsored by the European Community. A primary aim is to cultivate a deeper understanding of the parameters that govern the selectivities and stimulate a wider utilization of transition metal based catalysis in organic synthesis. All aspects of selectivity, chemo-, regio-, stereo- and enantioselectivity are considered and illustrated by applications in various fields or organic synthesis. The impact of catalysis in oxydation, reduction, carbonylation reactions, carbene chemistry, in Ni and Pd promoted dimerizations, oligomerizations as well as fonctionalisations is stressed, quite often with special emphasis laid on reaction mechanisms. In this aspect, the last chapter examplifies the interest of high pressure NMR and IR when investigating the nature of reaction intermediates in homogeneous reactions.

Inhalt
Industrial Aspects of Selectivity Applying Homogeneous Catalysis.- 1. Contributions of homogeneous catalysis to selectivity.- 2. Selectivity and homogeneous, industrial processes.- References.- To which Extent do Phosphanes Induce Selectivity in C?C Bond Formation?.- 1. Introduction.- 2. Structural, physical and bonding properties of phosphanes.- 3. Oligomerisation of alkenes.- 4. Oligomerisation of butadiene.- 5. Hydroformylation of alkenes.- 6. Conclusion.- References.- Ligand Controlled Catalysis: Chemo to Stereoselective Syntheses from Olefins and Dienes over Nickel Catalysts.- 1. Diene-olefin codimerization.- 2. Cyclodimerization of dienes.- 3. Linear dimerization of dienes.- 4. Concluding remarks.- References.- Catalytic Activation of Hydrogen Peroxide in Selective Oxidation Reactions.- 1. Introduction.- 2. General discussion on the activation of hydrogen peroxide.- 3. Practical applications.- 4. Conclusion and safety rules.- Acknowledgements.- References.- Enantioselective S-Oxidation: Synthetic Applications.- References.- Mechanisms in Stereo-Differentiating Metal-Catalyzed Reactions. Enantioselective Palladium-Catalyzed Allylation.- 1. The palladium-catalyzed substitution of allylic substrates by nucleophiles. The reaction. The catalytic steps.- 2. The stereochemical course of the reaction; analysis of the stereochemistry of each individual catalytic step.- 3. Enantioselective synthesis. Asymmetric induction.- References.- Regio-, Stereo-, and Enantioselectivity in Palladium and Platinum Catalyzed Organic Reactions.- 1. Introduction.- 2. Rearrangements.- 3. 1,4-Difunctionalization of 1,3-dienes.- 4. Cyclisation of non-conjugated dienes.- 5. Asymmetric alkylation via ?-allyl Pd complexes.- 6. Asymmetric hydroformylation.- References.- AsymmetricHydrogenation.- 1. Introduction.- 2. General principles.- 3. Asymmetric hydrogenation of substituted olefins.- 4. Asymmetric hydrogenation of carbon-oxygen double-bonds.- 5. Asymmetric hydrogenation of carbon-nitrogen double-bonds.- References.- The Design of a Chemoselective Reduction Catalyst.- 1. Introduction.- 2. Reduction of ?, ?-unsaturated ketones.- 3. Conclusions.- Acknowledgements.- References.- Palladium Catalyzed Reduction of Aryl Sulfonates Selectivity Control and Application to Anthracycline Chemistry.- References.- Selective Stoichiometric Reductions of Organic Functional Groups by Aqueous Metal Ions. Implications to Synthesis and Catalysis.- References.- Basic Principles in Carbene Chemistry and Applications to Organic Synthesis.- 1. Introduction.- 2. Basic principles of carbene reactivity.- 3. Methods for generating carbenes.- 4. Transition-metal-promoted carbene reactions.- 5. Applications.- 6. References.- Carbonylchromium (O) Complexes in Organic Synthesis.- 1. Arenetricarbonylchromium complexes.- 2. Pentacarbonylcarbene chromium complexes.- References.- Role and Implications of H+ and H? Anionic Hydrido Carbonyl Catalysts on Activity and Selectivity of Carbonylation Reactions of Unsaturated and Oxygenated Substrates.- 1. Hydroformylation of olefins.- 2. Hydrocarbonylation of oxygenated substrates with ruthenium catalysts.- 3. Hydrogenation of carbon monoxide.- Acknowledgements.- References.- Catalytic Carbonylations of Nitrogen Containing Organic Compounds.- 1. Introduction.- 2. Carbonylation of organic azides.- 3. Carbonylation of aromatic nitro compounds.- 4. Oxidative carbonylation of amines.- 5. Conclusions.- References.- Applications of Spectroscopic Measurements to Homogeneous Catalysis.- 1. Catalytic hydrogenation of alkenes.- 2. Rhodiumcatalysed asymmetric hydrogenation.- 3. Spectroscopic measurements under high pressure of gas.- 4. HPIR and HPNMR study of the reactions of [Rh4(CO)12?xLx], (x = 1 to 4; L = P{OPh}3) with CO, H2 or syngas.- 5. Conclusions.- Acknowledgements.- References.