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.

InhaltsangabeList of Contributors xv Preface xix 1 Phosphorus Ligand Effects in Homogeneous Catalysis and Rational Catalyst Design 1 Jason A. Gillespie, Erik Zuidema, Piet W. N. M. van Leeuwen, and Paul C. J. Kamer 1.1 Introduction 1 1.2 Properties of phosphorus ligands 7 1.3 Asymmetric ligands 15 1.4 Rational ligand design in nickel-catalysed hydrocyanation 19 1.5 Conclusions 22 References 23 2 Chiral Phosphines and Diphosphines 27 Wei Li and Xumu Zhang 2.1 Introduction 27 2.2 Chiral chelating diphosphines with a linking scaffold 30 2.3 Chiral atropisomeric biaryl diphosphines 46 2.4 Chiral phosphacyclic diphosphines 52 2.5 Pstereogenic diphosphine ligands 68 2.6 Experimental procedures for the syntheses of selected diphosphine ligands 69 2.7 Concluding remarks 75 References 75 3 Design and Synthesis of Phosphite Ligands for Homogeneous Catalysis 81 Aitor Gual, Cyril Goddard, Verónica de la Fuente, and Sergio Castillón 3.1 Introduction 81 3.2 Synthesis of phosphites 82 3.3 Highlights of catalytic applications of phosphite ligands 106 3.4 General synthetic procedures 122 References 124 4 Phosphoramidite Ligands 133 Laurent Lefort and Johannes G. de Vries 4.1 Introduction 133 4.2 Synthesis of phosphoramidites 134 4.3 Reactivity of the phosphoramidites 135 4.4 Types of phosphoramidite ligands 136 4.5 Conclusion 153 4.6 Synthetic procedures 153 References 153 5 Phosphinite and Phosphonite Ligands 159 T. V. (Babu) RajanBabu 5.1 Introduction 159 5.2 General methods for synthesis of complexes 160 5.3 Syntheses and applications of phosphinite ligands 162 in asymmetric catalysis 180 phosphinites 187 5.4 Synthesis and applications of phosphonite ligands 188 5.5 Experimental procedures for the syntheses of prototypical phosphinite and phosphonite ligands 208 2,6di O benzoyl a D glucopyranoside (Ligand 8) 209 phenyl]phosphino)4,6 O benzylideneglucopyranoside 211 [(2S,3R)3phenylthio4methylpent2oxy]diphenylphosphine 212 1methylethyl}4,5dihydrooxazole 214 phosphinite 215 4phosphabicyclo[5.3.0]decane 217 4phosphabicyclo/5.3.0]decane 218 [d1,2,f1,2]dioxaphosphe-pine 219 5.6 Acknowledgments 221 Abbreviations 221 References 222 6 Mixed Donor Ligands 233 René Tannert and Andreas Pfaltz 6.1 Introduction: general design principles 233 6.2 Synthesis of bidentate P,X-ligands 235 P,Nligands 243 6.3 Conclusion 257 6.4 Experimental procedures 257 References 260 7 Phospholes 267 Duncan Carmichael 7.1 Introduction 267 7.2 Creation of phospholes for use as ligands 269 7.3 Postsynthetic functionalisation 271 7.4 Phosphole coordination chemistry 273 7.5 Phospholes in catalysis 276 7.6 Experimental procedures 279 References 280 8 Phosphinine Ligands 287 Christian Müller 8.1 Introduction 287 8.2 Ligand properties 288 8.3 Synthesis of Phosphinines 292 8.4 Coordination chemistry 297 8.5 Reactivity of transition metal complexes 300 8.6 Application of phosphinines in homogeneous catalysis 300 8.7 Experimental procedure for the synthesis of selected phosphinines 303 References 305 9 Highly Strained Organophosphorus Compounds 309 J. Chris Slootweg 9.1 Introduction 309 9.2 Threemembered rings 310 9.3 Rearrangements 312 9.4 Homogeneous catalysis 313 9.5 Conclusions 314 9.6 Experimental procedures 315 References 317 10 Phosphaalkenes 321 Julien DugalTessier, Eamonn D. Conrad, Gregory R. Dake, and Derek P. Gates 10.1 Introduction 321 10.2 Synthesis of phosphaalkenes 324 10.3 Catalysis with phosphaalkene ligands 329 10.4 Concluding remarks 337 10.5 Experimental procedures for representative ligands 338 10.6 Acknowledgments 339 References 339 11 Phosphaalkynes 343 Christopher A. Russell and Nell S. Townsend 11.1 Introduction 343 11.2 General ex

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