Metal Promoted Selectivity in Organic Synthesis

Description

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. Front Matter....Pages i-xiii Industrial Aspects of Selectivity Applying Homogeneous Catalysis....Pages 1-15 To Which Extent do Phosphanes Induce Selectivity in C-C Bond Formation?....Pages 17-45 Ligand Controlled Catalysis: Chemo to Stereoselective Syntheses from Olefins and Dienes Over Nickel Catalysts....Pages 47-63 Catalytic Activation of Hydrogen Peroxide in Selective Oxidation Reactions....Pages 65-90 Enantioselective S -Oxidation: Synthetic Applications....Pages 91-105 Mechanisms in Stereo-Differentiating Metal-Catalyzed Reactions. Enantioselective Palladium-Catalyzed Allylation....Pages 107-131 Regio-, Stereo-, and Enantioselectivity in Palladium and Platinum Catalyzed Organic Reactions....Pages 133-159 Asymmetric Hydrogenation....Pages 161-189 The Design of a Chemoselective Reduction Catalyst....Pages 191-205 Palladium Catalyzed Reduction of Aryl Sulfonates. Selectivity Control and Application to Anthracycline Chemistry....Pages 207-222 Selective Stoichiometric Reductions of Organic Functional Groups by Aqueous Metal Ions. Implications to Synthesis and Catalysis....Pages 223-235 Basic Principles in Carbene Chemistry and Applications to Organic Synthesis....Pages 237-259 Carbonylchromium(O) Complexes in Organic Synthesis....Pages 261-286 Role and Implications of H + and H − Anionic Hydrido Carbonyl Catalysts on Activity and Selectivity of Carbonylation Reactions of Unsaturated and Oxygenated Substrates....Pages 287-310 Catalytic Carbonylations of Nitrogen Containing Organic Compounds....Pages 311-328 Applications of Spectroscopic Measurements to Homogeneous Catalysis....Pages 329-365 Back Matter....Pages 367-373