Organophosphorus Chemistry

From Molecules to Applications

Viktor Iaroshenko

• Publisher: Wiley-VCH
• Year: 2019
• Print ISBN: 9783527335725
• eBook ISBN: 9783527672264
• Edition: 1
• Topic: Physical Sciences
• Subtopic: Physical & Theoretical Chemistry

Filling the gap for an up-to-date reference that presents the field of organophosphorus chemistry in a comprehensive and clearly structured way, this one-stop source covers the chemistry, properties, and applications from life science and medicine. Divided into two parts, the first presents the chemistry of various phosphorus-containing compounds and their synthesis, including ylides, acids, and heterocycles. The second part then goes on to look at applications in life science and bioorganic chemistry. Last but not least, such important practical aspects as 31P-NMR and protecting strategies for these compounds are presented.

For organic, bioinorganic, and medicinal chemists, as well as those working on organometallics, and for materials scientists. The book, a contributed work, features a team of renowned scientists from around the world whose expertise spans the many aspects of modern organophosphorus chemistry.

1
Phosphines and Related Tervalent Phosphorus Systems: Organophosphorus Compounds as Ligands in Organometallic Catalysis

Piet W. N. M. van Leeuwen

LPCNO, INSA‐Toulouse, 135 Av. de Rangueil, 31077 Toulouse, France

1.1 Introduction

1.1.1 History

Phosphines and related phosphorus‐containing molecules play a major role in homogeneous catalysis. The history of homogeneous metal complex catalysis, as we know it today, started in the 1960s, although there had been even industrial applications long before that. In the 1920s, a catalytic process was used for the addition of water to acetylene. The metal mercury was used in a sulfuric acid solution. The reaction was very slow and large volumes were needed; thus, this was far from attractive. A related process still in operation is the zinc‐salt‐catalyzed addition of carboxylic acids to acetylene. With the introduction of petrochemistry, the feedstock for acetaldehyde production changed to ethene. The reaction used until today is a stoichiometric oxidation of ethene by palladium, the so‐called Wacker process, in which palladium is reoxidized with oxygen and a copper catalyst. Carbonylation catalysis came on stream in the 1930s and 1940s, although its application was retarded by World War II (WWII). Initially, the metals of choice were nickel, e.g. work by Reppe, and cobalt, especially hydroformylation by Roelen, and methanol carbonylation. Probably, Reppe (1948) was the first to use triphenylphosphine as a modifying ligand in a catalytic reaction, which concerned the addition of nickel‐cyanide‐catalyzed carbonylative alcohol addition to alkynes, leading to acrylates [1]. He used nickel cyanide also in the synthesis of polyketone from carbon monoxide and ethene in those early years. As of the 1960s, all these “leads” were greatly improved by ligand effects and by changing to the more active second‐row transition metals palladium and rhodium. Cobalt was also modified by phosphine ligands, and in this instance, the catalyst produced more of the linear oxygenate product, which now is mainly the alcohol rather than the aldehyde (Shell) [2]. Early examples of triphenylphosphine‐modified group 10 hydrogenation catalysis are due to Bailar and Itatani [3]. Ever since, more publications have appeared that reported phosphine effects on catalytic reactions.

1.1.2 Alternative Ligands

Before concentrating only on phosphorus ligands, we should mention that in the past three decades, ligands based on other donor atoms have become equally important and, in some areas, even more important than phosphines. In the mid‐1980s, the metallocene era started for the early transition metals especially in polymerization catalysis, followed by alkoxides, amides, and salen ligands. Meanwhile, metallocene catalysts have found industrial applications. In the late transition metal area, the diimine ligands stand out together with a shift to the first‐row metals for alkene polymerization, and they almost made it to a replacement of the nickel catalyst in the oligomerization of ethene. They were followed a little later by the outburst of the NHC ligands, which have beaten, in several instances, the best phosphines used so far in certain reactions. They have found commercial applications in metathesis reactions. A combination of all donor ligands in bidentates has further enriched the toolbox of homogeneous catalysis. One should not forget that the “ligand‐free” systems are attractive, as they do not suffer from ligand decomposition, but their life can still be limited because of precipitation or formation of a compound with the wrong valence state. The stabilizing ligands in these cases are, for example, carbon monoxide, alkenes, halides, and other anions, for example, the Wacker process, cobalt‐catalyzed hydroformylation (Exxon), nickel‐catalyzed oligomerization of butene to 3‐methylheptane (IFP, Dimersol process), rhodium‐catalyzed carbonylation of methanol (Monsanto, now BP), and ditto for iridium (BP, Cativa process).

1.1.3 Aim of the Chapter

The aim of this chapter is to give an introduction to the use of tervalent phosphorus comp...

Table of contents

• Cover
• Table of Contents
• 1 Phosphines and Related Tervalent Phosphorus Systems
• 2 Recent Developments in Phosphonium Chemistry
• 3 Phosphorus Ylides and Related Compounds
• 4 Low‐Coordinate Phosphorus Compounds with Phosphaorganic Multiple Bond Systems
• 5 Pentacoordinate Phosphorus Compounds
• 6 Hexacoordinate Phosphorus Compounds
• 7 Methods for the Introduction of the Phosphonate Moiety into Complex Organic Molecules
• 8 Phosphorus Heterocycles
• 9 Modern Aspects of 31P NMR Spectroscopy
• 10 Phosphorus in Chemical Biology and Medicinal Chemistry
• 11 Future Trends in Organophosphorus Chemistry
• Index
• End User License Agreement