Phosphorus(III)Ligands in Homogeneous Catalysis

Phosphorus(III)Ligands in Homogeneous Catalysis
Author: Paul C. J. Kamer
Publisher: John Wiley & Sons
Total Pages: 673
Release: 2012-05-09
Genre: Technology & Engineering
ISBN: 1118299701
GET BOOK

Over the last 60 years the increasing knowledge of transition metal chemistry has resulted in an enormous advance of homogeneous catalysis as an essential tool in both academic and industrial fields. Remarkably, phosphorus(III) donor ligands have played an important role in several of the acknowledged catalytic reactions. The positive effects of phosphine ligands in transition metal homogeneous catalysis have contributed largely to the evolution of the field into an indispensable tool in organic synthesis and the industrial production of chemicals. This book aims to address the design and synthesis of a comprehensive compilation of P(III) ligands for homogeneous catalysis. It not only focuses on the well-known traditional ligands that have been explored by catalysis researchers, but also includes promising ligand types that have traditionally been ignored mainly because of their challenging synthesis. Topics covered include ligand effects in homogeneous catalysis and rational catalyst design, P-stereogenic ligands, calixarenes, supramolecular approaches, solid phase synthesis, biological approaches, and solubility and separation. Ligand families covered in this book include phosphine, diphosphine, phosphite, diphosphite, phosphoramidite, phosphonite, phosphinite, phosphole, phosphinine, phosphinidenene, phosphaalkenes, phosphaalkynes, P-chiral ligands, and cage ligands. Each ligand class is accompanied by detailed and reliable synthetic procedures. Often the rate limiting step in the application of ligands in catalysis is the synthesis of the ligands themselves, which can often be very challenging and time consuming. This book will provide helpful advice as to the accessibility of ligands as well as their synthesis, thereby allowing researchers to make a more informed choice. Phosphorus(III) Ligands in Homogeneous Catalysis: Design and Synthesis is an essential overview of this important class of catalysts for academic and industrial researchers working in catalyst development, organometallic and synthetic chemistry.

New Aspects in Phosphorus Chemistry I

New Aspects in Phosphorus Chemistry I
Author: Jean-Pierre Majoral
Publisher: Springer
Total Pages: 250
Release: 2003-07-01
Genre: Science
ISBN: 3540457313
GET BOOK

Undoubtedly the chemistry of phosphorus appears more and more attractive in the sense that phosphorus presents an extraordinary versatile behaviour that allows the synthesis of a large number of different phosphorus reagents usable for applications in different fields, from biology to material science without f- getting key applications in catalysis. The full maturity of this topic of research can be explained by all the acquired knowledge over these twenty last years. Organic and inorganic chemistries of P , P and P species have been the s- in ]V v ject of thousands of publications while the chemistry of low coordinated ph- phorus derivatives experienced its hour of glory from the 1970s to the early 1990s. In parallel, interactions between phosphorus compounds and transition metals afforded many complexes, a lot of which present fascinating properties as catalysts. The interest in all these themes really is not decreasing, indeed some fas- nating areas of research are emerging or are the subject of many investigations: the medicinal chemistry of bisphosphonates, the role of phosphorus in biology, phosphorus ligands in radiopharmaceutical chemistry, phosphorus in material science, new polymers and dendrimers incorporating phosphorus, and as- metric catalysis to name but a few. Indeed researchers, benefitting from their background in basic phosphorus chemistry are developing many new fields of research.

Synthesis of New Phosphorus Ligands for Regioselective Hydroformylation

Synthesis of New Phosphorus Ligands for Regioselective Hydroformylation
Author: Yu-Ming Chie
Publisher:
Total Pages: 64
Release: 2010
Genre: Hydroformylation
ISBN:
GET BOOK

Tetraphosphorous ligands with enhanced chelating ability through multiple chelating modes and increased local phosphorus concentration can provide great regioselectivity in Rh/Ligand hydroformylation system. Here we report the synthesis of a series of pyrrole-based tetraphosphorus ligands were synthesized with introducing different functional groups into 3, 3', 5, 5'-positions of the biphenyl, and their applications to the hydroformylation of internal olefins, 1, 5-hexadiene, styrene and its derivatives, and alkyl acrylates. Internal olefins are cheaper and more readily available feedstock than terminal olefins, the development of highly selective and active isomerization-hydroformylation catalysts for internal olefins is of great importance from economic and energy points of view. In particular, the alkyl-substituted tetraphosphorous ligands gave the best results (for 2-octene, n: i up to 207, for 2-hexene, n: i up to 362). Double hydroformylation of 1, n-diolefins is a convenient method to produce dialdehydes. The hydroformylation of 1, 5- hexadiene can be achieved with essentially high regioselectivity (linear selectivity is up to 98%). Styrene and its derivatives prefer the branched aldehydes under the hydro-formylation conditions. However, the linear aldehydes can also be widely used for the production of detergents and plasticizers and important intermediates. Our studies on the hydroformylation of styrene and its derivatives achieved unprecedented high linear selectivity (l/b up to 22 for styrene). Hydroformylation of alkyl acrylate produces 1, 3- and1, 4-bifunctional compounds, which can be further converted into synthetically useful intermediates. Alkyl acrylates have been hydroformylated to the linear aldehydes with high regioselectivity (linear/branch> 99/1) and extraordinarily high average turnover frequencies (up to 5400 h 1) by using a rhodium complex with a tetraphosphorus ligand. The result is in sharp contrast to the most of other processes that favor production of the branched aldehyde (typically> 95% branched for most Rh-catalyzed reaction systems).