Phosphorus(iii)Ligands in Homogeneous Catalysis

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.

List of Contributors xvPreface xix1 Phosphorus Ligand Effects in Homogeneous Catalysis and Rational Catalyst Design 1Jason A. Gillespie, Erik Zuidema, Piet W. N. M. van Leeuwen, and Paul C. J. Kamer1.1 Introduction 11.2 Properties of phosphorus ligands 71.3 Asymmetric ligands 151.4 Rational ligand design in nickel-catalysed hydrocyanation 191.5 Conclusions 22References 232 Chiral Phosphines and Diphosphines 27Wei Li and Xumu Zhang2.1 Introduction 272.2 Chiral chelating diphosphines with a linking scaffold 302.3 Chiral atropisomeric biaryl diphosphines 462.4 Chiral phosphacyclic diphosphines 522.5 P-stereogenic diphosphine ligands 682.6 Experimental procedures for the syntheses of selected diphosphine ligands 692.7 Concluding remarks 75References 753 Design and Synthesis of Phosphite Ligands for Homogeneous Catalysis 81Aitor Gual, Cyril Goddard, Verónica de la Fuente, and Sergio Castillón3.1 Introduction 813.2 Synthesis of phosphites 823.3 Highlights of catalytic applications of phosphite ligands 1063.4 General synthetic procedures 122References 1244 Phosphoramidite Ligands 133Laurent Lefort and Johannes G. de Vries4.1 Introduction 1334.2 Synthesis of phosphoramidites 1344.3 Reactivity of the phosphoramidites 1354.4 Types of phosphoramidite ligands 1364.5 Conclusion 1534.6 Synthetic procedures 153References 1535 Phosphinite and Phosphonite Ligands 159T. V. (Babu) RajanBabu5.1 Introduction 1595.2 General methods for synthesis of complexes 1605.3 Syntheses and applications of phosphinite ligands 162in asymmetric catalysis 180phosphinites 1875.4 Synthesis and applications of phosphonite ligands 1885.5 Experimental procedures for the syntheses of prototypical phosphinite andphosphonite ligands 2082,6-di- O -benzoyl- a - D -glucopyranoside (Ligand 8) 209phenyl]-phosphino)-4,6- O -benzylidene-glucopyranoside 211[(2S,3R)-3-phenylthio-4-methylpent-2-oxy]diphenylphosphine 2121-methyl-ethyl}-4,5-dihydro-oxazole 214phosphinite 2154-phosphabicyclo[5.3.0]-decane 2174-phosphabicyclo/5.3.0]-decane 218[d1,2,f1,2]dioxaphosphe-pine 2195.6 Acknowledgments 221Abbreviations 221References 2226 Mixed Donor Ligands 233René Tannert and Andreas Pfaltz6.1 Introduction: general design principles 2336.2 Synthesis of bidentate P,X-ligands 235P,N-ligands 2436.3 Conclusion 2576.4 Experimental procedures 257References 2607 Phospholes 267Duncan Carmichael7.1 Introduction 2677.2 Creation of phospholes for use as ligands 2697.3 Postsynthetic functionalisation 2717.4 Phosphole coordination chemistry 2737.5 Phospholes in catalysis 2767.6 Experimental procedures 279References 2808 Phosphinine Ligands 287Christian Müller8.1 Introduction 2878.2 Ligand properties 2888.3 Synthesis of Phosphinines 2928.4 Coordination chemistry 2978.5 Reactivity of transition metal complexes 3008.6 Application of phosphinines in homogeneous catalysis 3008.7 Experimental procedure for the synthesis of selected phosphinines 303References 3059 Highly Strained Organophosphorus Compounds 309J. Chris Slootweg9.1 Introduction 3099.2 Three-membered rings 3109.3 Rearrangements 3129.4 Homogeneous catalysis 3139.5 Conclusions 3149.6 Experimental procedures 315References 31710 Phosphaalkenes 321Julien Dugal-Tessier, Eamonn D. Conrad, Gregory R. Dake, and Derek P. Gates10.1 Introduction 32110.2 Synthesis of phosphaalkenes 32410.3 Catalysis with phosphaalkene ligands 32910.4 Concluding remarks 33710.5 Experimental procedures for representative ligands 33810.6 Acknowledgments 339References 33911 Phosphaalkynes 343Christopher A. Russell and Nell S. Townsend11.1 Introduction 34311.2 General experimental 34411.3 Preparation of PC t Bu 344[2,2-dimethyl-1-(trimethylsiloxy)propylidene]-(trimethylsilyl) phosphine) 34611.4 Adamanylphosphaalkyne, AdC=P 34811.5 Mesitylphosphaalkyne, MesC=P 34911.6 Phospholide anions 350triphenylstannylphosphole 35211.7 1,3,5-Triphosphabenzene 352References 35312 P-chiral Ligands 355Jérôme Bayardon and Sylvain Jugé12.1 Introduction 35512.2 Designing P-chiral ligands using alcohols as chiral auxiliaries 35712.3 Designing P-chiral ligands using amino alcohols as chiral auxiliaries 36312.4 Designing of P-chiral ligands using amines as chiral auxiliaries 37712.5 Conclusion 38112.6 Experimental procedures 383References 38513 Phosphatrioxa-Adamantane Ligands 391Paul G. Pringle and Martin B. Smith13.1 Introduction 39113.2 Synthesis of phosphatrioxa-adamantanes 39313.3 Catalysis supported by phosphatrioxa-adamantane ligands 39513.4 Experimental procedures for phosphatrioxa-adamantanes ligands 401References 40214 Calixarene-based Phosphorus Ligands 405Angelica Marson, Piet W. N. M. van Leeuwen, and Paul C. J. Kamer14.1 Introduction 40514.2 Conformational properties 40714.3 Calixarene-based phosphorus ligands 40914.4 Applications in homogeneous catalysis 42214.5 Experimental procedures 424References 42515 Supramolecular Bidentate Phosphorus Ligands 427Jarl Ivar van der Vlugt and Joost N. H. Reek15.1 Introduction: general design principles 42715.2 Construction of bidentate phosphorus ligands via self-assembly 42915.3 Conclusions 44615.4 Experimental procedures 447References 45916 Solid-phase Synthesis of Ligands 463Michiel C. Samuels, Bert H. G. Swennenhuis, and Paul C. J. Kamer16.1 Introduction 46316.2 Insoluble supports in ligand synthesis 46616.3 Soluble polymeric supports 47016.4 Supported ligands in catalysis 47216.5 Solid-phase synthesis of nonsupported ligands 47316.6 Conclusions and outlook 47516.7 Experimental procedures 476References 47817 Biological Approaches 481René den Heeten, Paul C. J. Kamer, and Wouter Laan17.1 Introduction 48117.2 Peptide-based phosphine ligands 48117.3 Oligonucleotide-based phosphine ligands 48717.4 Phosphine-based artificial metalloenzymes 48817.5 Conclusions and outlook 49217.6 Representative synthetic procedures 493via hydrazone linkage 49417.7 Acknowledgments 495References 49518 The Design of Ligand Systems for Immobilisation in Novel Reaction Media 497Paul B. Webb and David J. Cole Hamilton18.1 Introduction 49718.2 Aqueous biphasic catalysis 49918.3 Fluorous biphasic catalysis 50318.4 Ionic liquids as reaction media 50718.5 Supercritical fluids as solvents in single- and multiphasic reaction systems 51218.6 Experimental section 518triphenylphosphine, TPPMS) 522([PrMIM][TPPMS]) 523bis (diphenylphosphino)-1,1'-binaphthyl ((R)-Rf-BINAP) 524References 526Index