van Leeuwen Homogeneous Catalysis

Understanding the Art
2004
ISBN: 978-1-4020-2000-1
Verlag: Springer Netherland
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 433 Seiten, eBook

No available as softcover

No other book available that gives insight into so many reactions of importance, while the field of homogeneous catalysis is becoming more and more important to organic chemists, industrial chemists, and academia.

 Gives real insight in the many new and old reactions of importance, based on the author's extensive experience in both teaching and industrial practice.

 Provide background to chemists trained in a different discipline and graduate and masters students who take catalysis as a main or secondary topic.

Zielgruppe

Research

Autoren/Hrsg.

van Leeuwen, Piet W.N.M.

Inhaltsverzeichnis

Preface.- Acknowledgements.- 1: Introduction.- 1.1. Catalysis. 1.2. Homogeneous catalysis. 1.3. Historical notes on homogeneous catalysis. 1.4. Characterization of the catalyst. 1.5. Ligand effects. 1.6. Ligands according to donor atoms. 2: Elementary Steps.- 2.1. Creation of a 'vacant' site and co-ordination of the substrate. 2.2. Insertion versus migration. 2.3. beta-Elimination and de-insertion. 2.4. Oxidative addition. 2.5. Reductive elimination. 2.6. alpha-Elimination reactions. 2.7. Cycloaddition reactions involving a metal. 2.8. Activation of a substrate toward nucleophilic attack. 2.9. sigma-Bond metathesis. 2.10. Dihydrogen activation. 2.11. Activation by Lewis acids. 2.12. Carbon-to-phosphorus bond breaking. 2.13. Carbon-to-sulfur bond breaking. 2.14. Radical reactions. 3: Kinetics.- 3.1. Introduction. 3.2. Two-step reaction scheme. 3.3. Simplifications of the rate equation and the rete-determining step. 3.4. Determining the selectivity. 3.5. Collection of rate data. 3.6. Irregularities in catalysis. 4: Hydrogenation.- 4.1. Wilkinson's catalyst. 4.2. Asymmetric hydrogenation. 4.3. Overview of chiral bidentate ligands. 4.4. Monodentate ligands. 4.5. Non-linear effects. 4.6. Hydrogen transfer. 5: Isomerisation.- 5.1. Hydrogen shifts. 5.2. Asymmetric isomerisation. 5.3. Oxygen shifts. 6: Carbonylation of Methanol and Methyl Acetate.- 6.1. Acetic acid. 6.2. Process scheme Monsanto process. 6.3. Acetic anhydride. 6.4. Other systems. 7: Cobalt Catalysed Hydroformylation.- 7.1. Introduction. 7.2. Thermodynamics. 7.3. Cobalt catalysed processes. 7.4. Cobalt catalysed processes for higher alkenes. 7.5. Kuhlmann cobalt hydroformylation process. 7.6. Phosphine modified cobalt catalysts: the shell process. 7.7. Cobalt carbonyl phosphine complexes. 8: Rhodium Catalysed Hydroformylation.- 8.1. Introduction. 8.2. Triphenylphosphine asthe ligand. 8.3. Diphosphines as ligands. 8.4. Phosphites as ligands. 8.5. Diphosphites. 8.6. Asymmetric hydroformylation. 9: Alkene Oligomerisation.- 9.1. Introduction. 9.2. Shell-higher-olefins-process. 9.3. Ethene trimerisation. 9.4. Other alkene oligomerisation reactions. 10: Propene Polymerisation.- 10.1. Introduction to polymer chemistry. 10.2. Mechanistic investigations. 10.3. Analysis by 13CNMR spectroscopy. 10.4. The development of metallocene catalysts. 10.5. Agostic interactions. 10.6. The effect of dihydrogen. 10.7. Further work using propene and other alkenes. 10.8. Non-metallocene ETM catalysts. 10.9. Late transition metal catalysts. 11: Hydrocyanation of Alkenes.- 11.1. The adiponitrile process. 11.2. Ligand effects. 12: Palladium Catalysed Carbonylations of Alkenes.- 12.1. Introduction. 12.2. Polyketone. 12.3. Ligand effects on chain length. 12.4. Ethene/propene/CO terpolymers. 12.5. Stereoselective styrene/CO terpolymers. 13: Palladium Catalysed Cross-Coupling Reactions.- 13.1. Introduction. 13.2. Allylic reaction. 13.3. Heck reaction. 13.4. Cross-coupling reaction. 13.5. Heteroatom-carbon bond formation. 13.6. Suzuki reaction. 14: Epoxidation.- 14.1. Ethene and propene oxide. 14.2. Asymmetric epoxidation. 14.3. Asymmetric hydroxilation of alkenes with osmium tetroxide. 14.4. Jacobsen asymmetric ring-opening of epoxides. 14.5. Epoxidations with dioxygen. 15: Oxydation with Dioxygen.- 15.1. Introduction. 15.2. The Wacker reaction. 15.3. Wacker type reactions. 15.4. Terephthalic acid. 15.5. PPO. 16: Alkene Metathesis.- 16.1. Introduction. 16.2. The mechanism. 16.3. Reaction overview. 16.4. Well-characterised tungsten and molybdenum catalysts. 16.5. Ruthenium catalysts. 16.6. Stereochemistry. 16.7. Catalyst decomposition. 16.8. Alkynes. 16.9. Industrial applications. 17: Enantioselective Cyclopropanation.-

Leseproben

Chapter 13
PALLADIUM CATALYSED CROSS-COUPLING REACTIONS (p. 271-272)

The new workhorse for organic synthesis

13. PALLADIUM CATALYSED CROSS-COUPLING REACTIONS

13.1 Introduction

The making of carbon-to-carbon bonds from carbocations and carbanions is a straightforward and simple reaction. Easily accessible carbanions are Grignard reagents RMgBr and lithium reagents RLi. They can be conveniently obtained from the halides RBr or RCl and the metals Mg and Li. They are both highly reactive materials, for instance with respect to water. The thermodynamic driving force for the formation of such reactive materials and their subsequent reactions is the formation of metal halides. The reactions of these carbon centred anions with polar compounds such as esters, ketones, and metal chlorides are indeed very specific and give high yields. The reaction of Grignard reagents with alkyl or aryl halides, however, is extremely slow giving many side-products, if anything happens at all. Note that this is also the key to the success of preparing Grignard type reagents(!), otherwise the partially formed RMgBr would react with the starting material RBr still present to give the "homocoupled" R-R. Exceptions are allylic and benzylic halides which react very fast amongst themselves during their synthesis. The Grignard reagents of this structure require specific practical procedures otherwise the homocoupled species are formed.

Reactions that can be expected for the reaction of an alkyl halide and a metal alkyl are depicted in Figure 13.1. The reaction may require several days at room temperature or may proceed in a few minutes, depending on the nature of the species. Many by-products may be formed. First a metal-halide exchange may occur. The resulting exchange products can give coupling products as well. Secondly, elimination reactions instead of C-C coupling can occur. Also, a radical reaction may take place. In summary, the yield and selectivity of this simple reaction will be surprisingly low. Only if a Grignard reagent is used in a coupling reaction with compounds that contain electrophilic carbon atoms, such as esters, ketones, and hetero-atom halides, the direct use of Grignard reagents (and related reagents) leads to high coupling efficiencies.

Figure 13.1. Products formed in a coupling reaction of a Grignard reagent and an alkyl halide

Thus, this reaction was of limited practical value until the transition metal catalysed cross-coupling reaction became known. Ever since, the "cross- coupling" reaction has found wide application in organic synthesis both in the laboratory and in industry. One might state that in any multi-step sequence for making an organic chemical, one of the steps involves a transition metal catalysed coupling reaction! The transition metal catalysts are usually based on palladium and sometimes nickel. In addition to organomagnesium and organolithium a great variety of organometallic precursors can be used. Also, many precursors can serve as starting materials for the carbocation. Last but not least, the ligand on the transition metal plays an important role in determining the rate and selectivity of the reaction. Here we will present only the main scheme and take palladium as the catalyst example, although many more metals have been found to be very useful. The reactions to be discussed are: allylic alkylation, Heck reaction, cross-coupling, and Suzuki reaction, a variant of the latter. Initially the cross-coupling chemistry focussed on carbon-tocarbon bond formation but in the last decade it has become also extremely useful for making carbon-to-heteroatom bonds. The organyl halide (or other anion used) involves in general an aryl, vinyl, or allylic species.