Homogeneous catalysis addition reactions

FIGURE 2.16. Homogeneous catalysis electrochemical reactions. Reaction scheme and typical cyclic voltammetric responses. The reversible wave pertains to the mediator alone. The dotted curve is the response of the substrate alone. The third voltammogram corresponds to the mediator after addition of the substrate. 

However, a number of limitations are still evident when tetrafluorohorate and hexafluorophosphate ionic liquids are used in homogeneous catalysis. The major aspect is that these anions are still relatively sensitive to hydrolysis. The tendency to anion hydrolysis is of course much less pronounced than that of the chloroalu-minate melts, hut it still occurs and this has major consequences for their use in transition metal catalysis. For example, the [PF ] anion of l-hutyl-3-methylimida-2olium ([BMIM]) hexafluorophosphate was found (in the author s laboratories) to hydrolyze completely after addition of excess water when the sample was kept for 8 h at 100 °C. Gaseous HF and phosphoric acid were formed. Under the same conditions, only small amounts of the tetrafluorohorate ion of [BMlMjjBFJ was converted into HF and boric acid [10]. The hydrolytic formation of HF from the anion of the ionic liquid under the reaction conditions causes the following problems with... 

Tamao K, Miyaura N (2002) Introduction to Cross-Coupling Reactions. 219 1-9 Tanaka M (2003) Homogeneous Catalysis for H-P Bond Addition Reactions. 232 25-54 Tanner PA (2004) Spectra, Energy Levels and Energy Transfer in High Symmetry Lanthanide Compounds. 241 167-278 ten Cate MGJ, see Crego-Calama M (2005) 249 in press ten Holte P,see Zwanenburg B (2001) 216 93-124 Thiem J,see Werschkun B (2001) 215 293-325... 

Much of the recent interest in insertion reactions undeniably stems from the emphasis placed on development of homogeneous catalysis as a rational discipline. One or more insertion is involved in such catalytic processes as the hydroformylation (31) or the polymerization of olefins 26, 75) and isocyanides 244). In addition, many insertion reactions have been successfully employed in organic and organometallic synthesis. The research in this general area has helped systematize a large body of previously unrelated facts and opened new areas of chemistry for investigation. Heck 114) and Lappert and Prokai 161) provide a comprehensive compilation and a systematic discussion of a wide variety of insertion reactions in two relatively recent (1965 and 1967) reviews. 

Tanaka M (2003) Homogeneous Catalysis for H-P Bond Addition Reactions. 232 25-54... 

In classical homogenous catalysis, an organic compound, i.e., a real liquid phase (a solvent) dissolves all of the reactants, catalysts, and products. The role of the solvent is underlined by the fact that it has to be separated from the reaction products by an additional and costly step, for example by distillation. 

Another solution to the problem of catalyst/product separation is the biphasic catalysis. The liquid biphasic catalysis became an attractive technology for potential commercial application of enantioselective homogeneous catalysis. The most important features of such systems are related to the fact that both reaction rate and e.s. may be influenced by the number of ionic groups in water-soluble ligand or by addition of surfactants. Descriptions of water-soluble ligands and the recent results in the rapidly progressing area of biphasic enantioselective catalysis are available in recent reviews [255,256],... 

The reaction between alkenes and synthesis gas (syngas), an equimolar mixture of carbon monoxide and hydrogen, to form aldehydes was discovered in 1938 by Otto Roelen [1,2]. Originally called oxo-reaction , hydroformyla-tion is the term used today. This reflects the formal addition of formaldehyde to the olefinic double bond. Commercially, homogeneous metal complexes based on cobalt and rhodium are used as catalysts. With more than 10 million metric tons of oxo products per year, this reaction represents the most important use of homogeneous catalysis in the chemical industry. 

The breaking of carbon-to-phosphorus bonds is by itself not a useful reaction in homogeneous catalysis. It is an undesirable side-reaction that occurs in systems containing transition metals and phosphine ligands and that leads to deactivation of the catalysts. Two reaction pathways can be distinguished, oxidative addition and nucleophilic attack at the co-ordinated phosphorus atom (Figure 2.35). 

In laboratory-scale homogeneous catalysis applications, in the last decade further investigations have been carried out in which a less soluble organo-metallic catalyst system was utilized for metathesis reactions [46]. Under RCM-conditions, it was possible to convert substrates with functional groups that were problematic due to their potential to inactivate the rutheniiun catalyst here, the conversion in supercritical carbon dioxide avoids the protection of critical amino groups as an additional synthetic step. Consequently, it was possible to synthesize a number of carbo- and heterocyclic products with varying ring size (C4 to Cie). 

In addition to the advantages listed, there are also some disadvantages that arise from the use of carbon dioxide as a reaction medium in homogeneous catalysis ... 

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