Metal Promoted Selectivity in Organic Synthesis

Industrial Aspects of Selectivity Applying Homogeneous Catalysis.- 1. Contributions of homogeneous catalysis to selectivity.- 1.1. Chemoselectivity.- 1.2. Regioselectivity.- 1.3. Stereoselectivity.- 1.4 Shapeselectivity.- 2. Selectivity and homogeneous, industrial processes.- 2.1. Optimal utilization of starting materials.- 2.2. Avoidance of by-products.- References.- To which Extent do Phosphanes Induce Selectivity in C?C Bond Formation?.- 1. Introduction.- 2. Structural, physical and bonding properties of phosphanes.- 2.1. The steric parameter ?: the cone angle.- 2.2. The electronic parameters.- 2.3. Bonding of phosphorus (III) ligands.- 2.3.1. Basicity of phosphines and ó-bonding.- 2.3.2. ?-Bonding.- 2.3.3. Separation of ?- and ?-bonding components.- 3. Oligomerisation of alkenes.- 3.1. Oligomerisation of ethylene.- 3.2. Oligomerisation of terminal alkenes.- 3.2.1. Propene.- 3.2.2. Styrene.- 3.2.3. Dimerisation of acrylates.- 4. Oligomerisation of butadiene.- 4.1. Influence of phosphanes on product distribution.- 4.2. Structure - selectivity relationships.- 4.3. Preparation of higher oligomers.- 5. Hydroformylation of alkenes.- 5.1. Tertiary-phosphine modified cobalt carbonyl systems.- 5.2. Tertiary-phosphine modified rhodium complexes.- 5.3. Two-phase hydroformylation.- 6. Conclusion.- References.- Ligand Controlled Catalysis: Chemo to Stereoselective Syntheses from Olefins and Dienes over Nickel Catalysts.- 1. Diene-olefin codimerization.- 1.1. Chemo and regioselective butadiene-ethylene codimerization.- 1.2. Butadiene-functionalized olefin codimerization.- 1.3. Asymmetric diene-olefin codimerization.- 1.3.1. Scope of the reaction.- 1.3.2. Aminophosphinephosphinites chelating ligands for cyclohexadiene-ethylene codimerization.- 2. Cyclodimerization of dienes.- 2.1. Scope of the reaction.- 2.2. Substituted conjugated dienes.- 2.3. Enantioselective cyclodimerizations.- 3. Linear dimerization of dienes.- 3.1. Linear dimerization of butadiene.- 3.2. Linear dimerization of alkyl substituted and functionalized dienes.- 3.3. Linear dimerization on nickel aminophosphinite complexes.- 3.3.1. Butadiene dimerization.- 3.3.2. Labelled experiments.- 3.3.3. Substituted dienes.- 3.3.4. Functionalized 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.- 2.1. Homolytic decomposition.- 2.2. Heterolytic decomposition.- 2.2.1. Natural activation.- 2.2.2. Catalytic activation.- 3. Practical applications.- 3.1. Oxidation of ketones to esters or lactones.- 3.2. Olefin epoxidation.- 3.3. Amines oxidation.- 3.3.1. Aromatic amines.- 3.3.2. Alipathic secondary amines.- 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.- 1.1. The ?3-allylpalladium forming steps (oxidative addition of the substrate to a palladium (0) complex). The reactive allylic compounds.- 1.2. The nucleophilic attack step. The active nucleophiles.- 2. The stereochemical course of the reaction; analysis of the stereochemistry of each individual catalytic step.- 2.1. The ?3-allyl forming step is under stereoelectronic control; stereochemical requirements for the allylic substrate to be reactive.- 2.2. The use of properly devised models to appreciate the way of attack of the nucleophile.- 3. Enantioselective synthesis. Asymmetric induction.- 3.1. Optically active substrates the chiral director is located in the substrate.- 3.1.1. As the leaving group.- 3.1.2. In the allylic frame.- 3.2. Optically active nucleophiles. The chiral inducer is located in the nucleophile.- 3.3. Optically active catalysts.