Aspects of Homogeneous Catalysis, Softcover reprint of the original 1st ed. 1984
A Series of Advances
Coll. Aspects of Homogeneous Catalysis, Vol. 5

1. INTRODUCTION Although quite spectacular results have been obtained in the last few decades in the field of homogeneous transition metal catalyzed transformations of olefins and alkynes [1], reactions which could lead to heterocycles have been partly neglected. An obvious reason for this is that substrates containing heteroatoms such as N, 0 or S could coordinate the metal and suppress the catalytic activity. Nevertheless, some interesting early examples of transition-metal-catalyzed syntheses of heterocyclic compounds have been reported and these have been reviewed by C. W. Bird [2] . More recently the incorporation of CO , which enables esters and lactones 2 to be synthesized from olefinic starting materials, has begun to attract attention (see, for example, ref. [3]). The dominant role of palladium as the catalyst for the formation of O-containing heterocycles has been suggested to be associated with the relatively low strength of the Pd-O bond. Among the first examples of a nitrogen-containing heterocycle to be formed by homogeneous catalysis is the triazine shown in Equation 1 which is the product of the trimerization of benzonitrile in the presence of iron penta carbonyl or Raney­ nickel [4] .

of Volume 5.- Telomerization of Dienes by Homogeneous Transition Metal Catalysts.- 1. Introduction.- 2. Telomerization of Butadiene.- 3. Telomerization of Isoprene.- 4. Telomerization of Further 1,3-Dienes.- 5. Telomerization of 1,2-Dienes.- 6. Cotelomerizations.- 7. Acknowledgement.- 8. References.- The Cobalt-Catalyzed Synthesis of Pyridine and Its Derivatives.- 1. Introduction.- 2. Survey of the Organocobalt Catalysts.- 3. The Application of the Cobalt-Catalyzed Pyridine Synthesis.- 4. Experimental Details.- 5. Mechanistic Considerations.- 6. Experimental Optimization of the Catalytic Turnover Number.- 7. Synthesis of the Catalysts.- 8. Related Reactions.- 9. Acknowledgement.- 10. Glossary of Abbreviations.- 11. References.- Homogeneous Catalysis Using Iodide-Promoted Rhodium Catalysts.- 1. Introduction.- 2. Rhodium Iodocarbonyls.- 3. Catalysis of the Water Gas Shift Reaction.- 4. Alcohol Carbonylation.- 5. Carbonylation of Esters and Ethers.- 6. Reductive Carbonylation of Esters and Ethers.- 7. Hydrocarboxylation of Olefins.- 8. Hydrocarboxylation of Formaldehyde.- 9. Hydrogenolysis Reactions.- 10. Homologation of Carboxylic Acids.- 11. Heterogenisation of the Rh/I Catalyst.- 12. Conclusions.- 13. References.- Recent Developments in the Homogeneous Catalysis of the Water-Gas Shift Reaction.- 1. Introduction.- 2. Background.- 3. Chemistry of the WGSR Catalytic Cycles.- 4. Catalysis of the WGSR under Basic Conditions.- 5. Catalysis of the WGSR under Acidic or Neutral Conditions.- 6. References.- Homologation of Alcohols, Acids and Their Derivatives by CO + H2.- 1. Introduction.- 2. Homologation of Alcohols.- 3. Carbonylation and Homologation of Ethers.- 4. Homologation of Aldehydes.- 5. Homologation of Carboxylic Acids.- 6. Homologation of Carboxylic Acid Esters.- 7. Homologation Reactions with Heterogeneous Catalysts.- 8. Homologation Reactions with CO and H2O.- 9. Reaction Mechanism.- 10. Concluding Remarks.- 11. Addendum.- 12. Glossary of Abbreviations.- 13. References.