Catalysis by Metal Complexes

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 o-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. The chiral inducer is located in the ligand of the catalyst.- 3.3.1. The substrate is achiral, non-prochiral; the nucleophile is prochiral.- 3.3.2. The substrate is prochiral, chiral or achiral; the nucleophile is not prochiral.- 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.- 4.1. Organopalladation of non-conjugated dienes.- 4.2. Ene reaction of dienes and olefins coupling reactions.- 5. Asymmetric alkylation via ?-allyl Pd complexes.- 6. Asymmetric hydroformylation.- References.- Asymmetric Hydrogenation.- 1. Introduction.- 2. General principles.- 2.1. Chiral phosphine ligands.- 2.2. Structure of the substrates.- 2.3. Stereochemistry of the hydrogenations.- 2.4. Mechanism of the hydrogenations with rhodium (I)- and iridium (I)-catalysts.- 2.4.1. Hydrogenation of substrates with directing groups.- 2.4.2. Hydrogenation of substrates without directing groups.- 2.5. Hydrogenations with ruthenium-catalysts.- 3. Asymmetric hydrogenation of substituted olefins.- 3.1. Amino acid precursors.- 3.2. (Z)-enamides.- 3.3. Unsaturated carboxylic acid derivatives.- 3.4. ?,?-unsaturated aldehydes and ketones.- 3.5. Allylic and homoallylic alchohols.- 4. Asymmetric hydrogenation of carbon-oxygen double-bonds.- 4.1. ?-ketoachid derivatives.- 4.2. Hydrogenation of ?-keto compounds.- 4.3. Alkylamino aryl ketones.- 4.4. Ketones.- 5. Asymmetric hydrogenation of carbon-nitrogen double-bonds.- References.- The Design of a Chemoselective Reduction Catalyst.- 1. Introduction.- 2. Reduction of ?, ?-unsaturated ketones.- 2.1. Hydrogenation reactions.- 2.1.1. Hydrogenation with iridium/monophosphine systems.- 2.1.2. Hydrogenation with iridium/diphosphine systems.- 2.1.3. Hydrogenation with iridium/P?N systems.- 2.2. Hydrogen transfer reactions: catalysis by iridium/P?N systems.- 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.- 4.1. Recations of carbenoids.- 4.1.1. The catalytic cycle.- 4.1.2. Factors governing the catalytic activity.- 4.1.3. Typical catalysts.- 4.1.4. Typical ligands.- 4.2. Selectivities in catalysed carbene reactions.- 4.2.1. Stereo selectivity.- 4.2.1.1. Enantioselectivity.- 4.2.1.2. Cis to trans selectivity.- 4.2.2. Regioselectivity and discrimination between different substrates and functions.- a. Regioselectivity.- b. Discrimination.- c Competition.- d. Regioselectivity and discrimination in the Buchner's reaction.- e. Discrimination between different functionalities: chemo-selectivity.- 5. Applications.- 6. References.- Carbonylchromium (O) Complexes in Organic Synthesis.- 1. Arenetricarbonylchromium complexes.- 1.1. Methods of preparation and decomplexation.- 1.2. Effects of coordination of arenes to Cr(CO)3.- 1.3. Stabilization of benzylic carbanion.- 1.4. Metallation of the complexed arenas.- 1.5. Nucleophilic attack on ?6-arene Cr(CO)3 complexes.- 1.6. Asymmetric chromiumtricarbonyl arene derivatives.- 2. Pentacarbonylcarbene chromium complexes.- 2.1. Synthesis of carbene complexes.- 2.2. Reactivity of carbene 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.- 1.1. Preamble.- 1.2. Application of NMR spectroscopy in determining chemical exchange.- 1.3. Ligand exchange in [RhCl(PPh3)3].- 1.4. Ligand exchange in [RhH2Cl(PPh3)3].- 1.5. Reversibility of H2 uptake in oxidative-addition reactions determined via para-hydrogen induced polarization.- 2. Rhodium catalysed asymmetric hydrogenation.- 2.1. Mechanism of interconversion of the diastereoisomeric complexes (12) and (12?).- 2.2. Stereochemistry of the hydrogenated intermediates.- 3. Spectroscopic measurements under high pressure of gas.- 3.1. IR (HPIR).- 3.2. NMR (HPNMR).- 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.- 4.1. Introduction.- 4.2. Reaction of [Rh4(CO)8{P(OPh)3}4] with CO.- 4.3. Reaction of [Rh4(CO)11 {P(OPh)3}] with CO.- 4.4. Reaction of [Rh4(CO)9{P(OPh)3}3] with CO.- 4.5. Fluxionality in [Rh2(CO)6{P(OPh)3}2] and [Rh2(CO)7{P(OPh)3}].- 5. Conclusions.- Acknowledgements.- References.