Phosphorus(III)Ligands in Homogeneous Catalysis
Design and Synthesis
1. Edition June 2012
566 Pages, Hardcover
Wiley & Sons Ltd
Short Description
This book addresses the design and synthesis of a comprehensive compilation of phosphorous(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. This reference offers an essential overview of this important class of catalysts for academic and industrial researchers working in catalyst development, organometallic, and synthetic chemistry.
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.
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 P-stereogenic 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
2,6-di- O -benzoyl- a - D -glucopyranoside (Ligand 8) 209
phenyl]-phosphino)-4,6- O -benzylidene-glucopyranoside 211
[(2S,3R)-3-phenylthio-4-methylpent-2-oxy]diphenylphosphine 212
1-methyl-ethyl}-4,5-dihydro-oxazole 214
phosphinite 215
4-phosphabicyclo[5.3.0]-decane 217
4-phosphabicyclo/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,N-ligands 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 Three-membered 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 Dugal-Tessier, 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 experimental 344
11.3 Preparation of PC t Bu 344
[2,2-dimethyl-1-(trimethylsiloxy)propylidene]-(trimethylsilyl) phosphine) 346
11.4 Adamanylphosphaalkyne, AdC=P 348
11.5 Mesitylphosphaalkyne, MesC=P 349
11.6 Phospholide anions 350
triphenylstannylphosphole 352
11.7 1,3,5-Triphosphabenzene 352
References 353
12 P-chiral Ligands 355
Jérôme Bayardon and Sylvain Jugé
12.1 Introduction 355
12.2 Designing P-chiral ligands using alcohols as chiral auxiliaries 357
12.3 Designing P-chiral ligands using amino alcohols as chiral auxiliaries 363
12.4 Designing of P-chiral ligands using amines as chiral auxiliaries 377
12.5 Conclusion 381
12.6 Experimental procedures 383
References 385
13 Phosphatrioxa-Adamantane Ligands 391
Paul G. Pringle and Martin B. Smith
13.1 Introduction 391
13.2 Synthesis of phosphatrioxa-adamantanes 393
13.3 Catalysis supported by phosphatrioxa-adamantane ligands 395
13.4 Experimental procedures for phosphatrioxa-adamantanes ligands 401
References 402
14 Calixarene-based Phosphorus Ligands 405
Angelica Marson, Piet W. N. M. van Leeuwen, and Paul C. J. Kamer
14.1 Introduction 405
14.2 Conformational properties 407
14.3 Calixarene-based phosphorus ligands 409
14.4 Applications in homogeneous catalysis 422
14.5 Experimental procedures 424
References 425
15 Supramolecular Bidentate Phosphorus Ligands 427
Jarl Ivar van der Vlugt and Joost N. H. Reek
15.1 Introduction: general design principles 427
15.2 Construction of bidentate phosphorus ligands via self-assembly 429
15.3 Conclusions 446
15.4 Experimental procedures 447
References 459
16 Solid-phase Synthesis of Ligands 463
Michiel C. Samuels, Bert H. G. Swennenhuis, and Paul C. J. Kamer
16.1 Introduction 463
16.2 Insoluble supports in ligand synthesis 466
16.3 Soluble polymeric supports 470
16.4 Supported ligands in catalysis 472
16.5 Solid-phase synthesis of nonsupported ligands 473
16.6 Conclusions and outlook 475
16.7 Experimental procedures 476
References 478
17 Biological Approaches 481
René den Heeten, Paul C. J. Kamer, and Wouter Laan
17.1 Introduction 481
17.2 Peptide-based phosphine ligands 481
17.3 Oligonucleotide-based phosphine ligands 487
17.4 Phosphine-based artificial metalloenzymes 488
17.5 Conclusions and outlook 492
17.6 Representative synthetic procedures 493
via hydrazone linkage 494
17.7 Acknowledgments 495
References 495
18 The Design of Ligand Systems for Immobilisation in Novel Reaction Media 497
Paul B. Webb and David J. Cole Hamilton
18.1 Introduction 497
18.2 Aqueous biphasic catalysis 499
18.3 Fluorous biphasic catalysis 503
18.4 Ionic liquids as reaction media 507
18.5 Supercritical fluids as solvents in single- and multiphasic reaction systems 512
18.6 Experimental section 518
triphenylphosphine, TPPMS) 522
([PrMIM][TPPMS]) 523
bis (diphenylphosphino)-1,1'-binaphthyl ((R)-Rf-BINAP) 524
References 526
Index
