Filling a gap in the market for an up-to-date work on the topic, this unique and timely book in 2 volumes is comprehensive in covering the entire range of fundamental and applied aspects of hydroformylation reactions.
The two authors are at the forefront of catalysis research, and unite here their expertise in synthetic and applied catalysis, as well as theoretical and analytical chemistry. They provide a detailed account of the catalytic systems employed, catalyst stability and recovery, mechanistic investigations, substrate scope, and technical implementation. Chapters on multiphase hydroformylation procedures, tandem hydroformylations and other industrially applied reactions using syngas and carbon monoxide are also included.
The result is a must-have reference not only for synthetic chemists working in both academic and industrial research, but also for theoreticians and analytical chemists.

Armin Börner studied education and chemistry at the University of Rostock and completed his PhD thesis in the group of Prof. Dr. H. Kristen in 1984. Between 1984 and 1992 he was a scientific co-worker in the field of complex catalysis at the Academia of Science under Prof. Dr. H. Pracejus. After a postdoctoral term in the group of Prof. Dr. H. B. Kagan in Orsay, France, he relocated to the Max-Planck-Group for Asymmetric Catalysis in Rostock in 1993, where he was awarded his professorial research degree (habilitation) in 1995. Since 2000 he has been Professor of Organic Chemistry at the University of Rostock and head of a research department at the Leibniz-Institute for Catalysis (LIKAT) Rostock. His research focuses on applied homogeneous catalysis and he has published over 250 scientific papers, reviews, book chapters and patents. More than 15 catalytic processes and analytical tools which have been developed in his department are running in a technical scale or have been commercialized.

Robert Franke studied chemistry at Bochum University, Germany. He earned his doctorate degree in 1994 in the field of relativistic quantum chemistry under Prof. Dr. W. Kutzelnigg. After working for a period as a research assistant, he joined the process engineering department of the former Huls AG in Germany, a predecessor company of Evonik Performance Materials GmbH, in 1998. He is now Director Innovation Management Hydroformylation. He was awarded his professorial research degree (habilitation) in 2002, since when he has taught at the University of Bochum. In 2011 he was made adjunct professor. His research focuses on homogeneous catalysis, process intensification, and computational chemistry. He has published over 150 scientific papers, reviews, book chapters and patents.

One of the largest industrial applications of homogeneous catalysis, hydroformylation is the process whereby alkenes react with carbon monoxide and hydrogen at high temperatures in the presence of a transition metal catalyst to yield aldehydes. The resulting products are valuable intermediates in the synthesis of alcohols, esters, amines, and olefins, used in pharmaceutical chemistry and the manufacture of fragrances. This reaction was discovered around 70 years ago, and nowadays some ten million metric tons of aldehydes are produced each year.

This up-to-date reference is unique in its comprehensive coverage from fundamentals to applications, summarizing the latest advances and developments in hydroformylation reactions. The two authors are at the forefront of catalysis research, and unite their expertise in synthetic and applied catalysis, as well as theoretical and analytical chemistry.

As such, they provide a detailed account of the catalytic systems employed, catalyst stability and recovery, mechanistic investigations, substrate scope, and technical implementation. Chapters on multiphase hydroformylation procedures, tandem hydroformylations and other industrially applied reactions using syngas and carbon monoxide are also included.

A must-have reference not only for synthetic chemists working in academic and industrial research, but also for theoreticians and analytical chemists.

Volume 1

Foreword xi

Introduction 1

References 3

1 Metals in Hydroformylation 5

1.1 The Pivotal Role of Hydrido Complexes 5

References 8

1.2 Bimetallic Catalysts 9

References 10

1.3 Effect of Organic Ligands 10

References 14

1.4 Cobalt-Catalyzed Hydroformylation 15

1.4.1 History and General Remarks 15

1.4.2 The Mechanism, Catalysts, and Ligands 16

1.4.3 Some Recent and Special Applications 20

References 23

1.5 Rhodium-Catalyzed Hydroformylation 24

1.5.1 History and Technical Importance 24

1.5.2 Catalyst Precursors 26

1.5.3 Summary and Conclusions 32

References 32

1.6 Ruthenium-Catalyzed Hydroformylation 36

1.6.1 General Aspects 36

1.6.2 Catalyst Precursors 37

1.6.3 Ligands 38

1.6.4 Mechanistic Considerations 42

1.6.5 Hydroformylation Using the Reversed Water Gas Shift (RWGS) or Methyl Formate 43

1.6.6 Domino Reactions with Ru Catalysts 44

References 46

1.7 Palladium-Catalyzed Hydroformylation 48

1.7.1 General Aspects 48

1.7.2 Mechanistic Investigations, Complexes, and Ligands 48

1.7.3 Some Applications 50

References 51

1.8 Platinum-Catalyzed Hydroformylation 52

1.8.1 General Aspects 52

1.8.2 Mechanistic Investigations, Complexes, and Ligands 53

1.8.3 Some Applications 57

References 60

1.9 Iridium-Catalyzed Hydroformylation 62

1.9.1 General Aspects 62

1.9.2 Mechanistic Investigations, Complexes, and Ligands 62

1.9.3 Some Applications 65

References 66

1.10 Iron-Catalyzed Hydroformylation 67

1.10.1 General Aspects 67

1.10.2 Monometallic Iron Catalysts 67

1.10.3 Iron Complexes as Additives to Conventional Hydroformylation Catalysts 69

References 70

2 Organic Ligands 73

References 77

2.1 Phosphines Typical Structures and Individuals, Syntheses, and Selected Properties 78

2.1.1 Monodentate Phosphines 78

2.1.2 Diphosphines 86

2.1.3 Triphosphines 91

2.1.4 Tetraphosphines 93

2.1.5 Ligands for Special Applications 95

2.1.5.1 Phosphines with Improved Solubility in Aromatic Solvents 96

2.1.5.2 Phosphines-Bearing Functional Groups 97

2.1.5.3 Phosphines Designed for Hydroformylation in Ionic Liquids (ILs) 102

2.1.5.4 Dendrimers as Support for Phosphines 105

2.1.5.5 Polymer-Supported Phosphines 114

2.1.6 Decomposition of Phosphines 118

2.1.6.1 Enemies of Phosphines in the Absence of the Metal 120

2.1.6.2 Decomposition of Phosphines in the Presence of Metals 122

References 128

2.2 Phosphites Synthesis, Typical Examples, and Degradation 136

2.2.1 General Aspects 136

2.2.2 Synthesis of Alcohols 138

2.2.2.1 Mono-, Bi-, and Polyphenols 138

2.2.2.2 Benzylic Alcohols 145

2.2.2.3 Aliphatic Diols 146

2.2.3 Synthesis of Phosphites Typical Routes and Problems 150

2.2.4 Types and Selected Ligands 158

2.2.4.1 Mono-, Di-, and Triphosphites 158

2.2.4.2 Polyphosphites Linked to Supports 162

2.2.5 Stereochemical Considerations 162

2.2.6 StructureActivity Relationships in Hydroformylation 166

2.2.7 Rhodium Phosphite Precatalysts 167

2.2.8 Degradation Pathways of Phosphites 169

2.2.8.1 Reaction with Oxygen and Peroxides 169

2.2.8.2 Reaction with Water 170

2.2.8.3 Reaction with Alcohols 176

2.2.8.4 Degradation with Acids 176

2.2.8.5 Degradation and Consequences for Rhodium Complex Formation 178

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