List 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
1.2.1 Electronic ligand parameters 7
1.2.2 Steric ligand parameters 9
1.2.3 Bite angle effects 10
1.2.3.1 Electronic bite angle effect 11
1.2.3.2 Steric bite angle effect 12
1.2.3.3 Steric versus electronic bite angle effects 12
1.2.4 Molecular electrostatic potential (MESP) approach 13
1.3 Asymmetric ligands 15
1.4 Rational ligand design in nickel-catalysed hydrocyanation 19
1.4.1 Introduction 19
1.4.2 Mechanistic insights 20
1.4.3 Rational design 20
1.5 Conclusions 22
References 23
2 Chiral Phosphines and Diphosphines 27
Wei Li and Xumu Zhang
2.1 Introduction 27
2.1.1 Early developments 27
2.2 Chiral chelating diphosphines with a linking scaffold 30
2.2.1 Building chiral backbones from naturally available materials 30
2.2.1.1 Early development 30
2.2.1.2 Syntheses of DIOP variants 31
2.2.1.3 Synthesis from other natural chiral backbones 33
2.2.2 Design and synthesis of chiral backbones 35
2.2.2.1 Chiral backbones synthesized through asymmetric catalysis 35
2.2.2.2 Design and synthesis of ligands containing spiro backbones 37
2.2.2.3 Design and synthesis of chiral ferrocene backbones 40
2.2.2.4 Design and synthesis of other chiral backbones 41
2.2.3 Synthesis from optical resolution of phosphine precursors or intermediates 43
2.3 Chiral atropisomeric biaryl diphosphines 46
2.3.1 Synthesis of BINAP and its derivatives 46
2.3.2 Synthesis of atropisomeric biaryl ligands 49
2.3.3 General strategies of synthesizing of atropisomeric biaryl ligands 52
2.4 Chiral phosphacyclic diphosphines 52
2.4.1 Fundamental discovery and syntheses of BPE and DuPhos 52
2.4.2 Design and synthesis of bisphosphetanes 56
2.4.3 Design and synthesis of bisphospholanes 58
2.4.3.1 BPE and DuPhos analogue ligands 58
2.4.3.2 P-stereogenic bisphospholane ligands 60
2.4.4 Design and synthesis of bisphospholes 63
2.4.5 Design and synthesis of bisphosphinanes 65
2.4.6 Design and synthesis of bisphosphepines 66
2.4.7 Summary of synthetic strategies of phosphacycles 68
2.5 P-stereogenic diphosphine ligands 68
2.6 Experimental procedures for the syntheses of selected diphosphine ligands 69
2.6.1 Synthesis procedure for DIOP* ligand 69
2.6.2 Synthesis procedure of SDP ligands 70
2.6.3 Synthesis procedure of (R ,R )-BICP 71
2.6.4 Synthesis procedure of SEGPHOS 71
2.6.5 Synthesis procedure of Ph-BPE 72
2.6.6 Synthesis procedure of TangPhos 73
2.6.7 Synthesis procedure of Binaphane 74
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
3.2.1 Monophosphites 82
3.2.1.1 Symmetrically substituted monophosphites 82
3.2.1.2 Nonsymmetrically substituted monophosphites 83
3.2.1.3 Caged monophosphites 84
3.2.1.4 Monophosphites bearing dioxaphospho-cyclic units 84
3.2.2 Diphosphite ligands 94
3.2.2.1 Diphosphites not containing a dioxaphospho-cyclic unit 94
3.2.2.2 Diphosphites bearing dioxaphospho-cyclic units 95
3.2.3 Triphosphites 105
3.3 Highlights of catalytic applications of phosphite ligands 106
3.3.1 Hydrogenation reactions 106
3.3.2 Functionalization of alkenes: hydroformylation and hydrocyanation 108
3.3.2.1 Hydroformylation 108
3.3.2.2 Hydrocyanation 110
3.3.3 Addition of nucleophiles to carbonyl compounds and derivatives 110
3.3.3.1 1,2-addition 111
3.3.3.2 1,4-addition 111
3.3.4 Allylic substitution reactions 113
3.3.5 Miscellaneous reactions 117
3.4 General synthetic procedures 122
3.4.1 Symmetrically substituted phosphites 122
3.4.2 Nonsymmetrically substituted phosphites 123
3.4.3 Phosphites bearing dioxaphospho-cyclic units 123
References 124
4 Phosphoramidite Ligands 133
Laurent Lefort and Johannes G. de Vries
4.1 Introduction 133
4.1.1 History 134
4.2 Synthesis of phosphoramidites 134
4.3 Reactivity of the phosphoramidites 135
4.4 Types of phosphoramidite ligands 136
4.4.1 Acyclic monodentate phosphoramidites 136
4.4.2 Cyclic monodentate phosphoramidites based on diols 136
4.4.2.1 Synthesis of binaphthol- and biphenol-based phosphoramidites 137
4.4.2.2 Synthesis of TADDOL-based phosphoramidites 140
4.4.2.3 Synthesis of spiro-based phosphoramidites 141
4.4.2.4 Synthesis of 1,2-diol-based phosphoramidites 141
4.4.2.5 Phosphoramidites based on unusual diols 141
4.4.3 Cyclic phosphoramidites based on amino alcohols 142
4.4.4 Bis-phosphoramidites 143
4.4.4.1 Bis-phosphoramidites based on diamines 143
4.4.4.2 Bis-phosphoramidites based on diols 144
4.4.4.3 Other bidentate phosphoramidites 145
4.4.5 Mixed bidentate ligands 145
4.4.5.1 Phosphoramiditephosphines 145
4.4.5.2 Phosphoramiditephosphite 147
4.4.5.3 Phosphoramiditeamines 148
4.4.5.4 Other bidentate phosphoramidite ligands 149
4.4.6 Polydendate phosphoramidites 149
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
5.3.1 Early studies 162
5.3.2 Phosphinite ligands from carbohydrates 163
5.3.2.1 Rh-catalyzed asymmetric hydrogenation of dehydroaminoacids 164
5.3.2.2 Ni(0)-catalyzed asymmetric hydrocyanation 166
5.3.2.3 Ni(0)- and Pd(0)-catalyzed allylic substitution by carbon nucleophiles 170
5.3.2.4 Rh(I)-catalyzed hydroformylation of vinylarenes 171
5.3.2.5 Ni(II)-catalyzed asymmetric hydrovinylation of alkenes 171
5.3.2.6 Ligands for homogeneous catalysis in water 172
5.3.3 Phosphinite ligands from other alcohols 172
5.3.4 Phosphinephosphinite and aminephosphinite ligands 173
5.3.5 Phosphinites from amines, amino alcohols, and amino acids 174
5.3.5.1 Aminophosphines 174
5.3.5.2 Aminophosphinephosphinite (AMPP) ligands 176
5.3.6 Bisphosphinite ligands with other scaffoldings 179
5.3.7 1,1'-Diaryl-2,2'-phosphinites and dynamic conformational control
in asymmetric catalysis 180
5.3.8 Monophosphinite ligands 182
5.3.9 Hybrid ligands containing phosphinites 182
5.3.9.1 Thioetherphosphinite ligands 182
5.3.9.2 Oxazolinephosphinite and pyridinephosphinite ligands 184
5.3.9.3 An alkenephosphinite ligand 186
5.3.9.4 Chiral transition metal Lewis acids bearing electron-withdrawing
phosphinites 187
5.4 Synthesis and applications of phosphonite ligands 188
5.4.1 Early studies 188
5.4.2 Phosphonites from TADDOL and related compounds 189
5.4.3 Phosphonites derived from 2,2'-hydroxybiaryls and related compounds 193
5.4.4 Phosphinephosphonite ligands 196
5.4.5 Phosphonites with paracyclophane backbone 196
5.4.6 Phosphonites with a spirobisindane backbone 197
5.4.7 Miscellaneous phosphonite ligands 198
5.4.8 Development of phosphonite ligands for industrially relevant processes 199
5.4.8.1 Phosphonite ligands in hydroformylation 199
5.4.8.2 Phosphonite ligands in Ni(0)-catalyzed hydrocyanation 201
5.4.8.3 Oxazolinephosphonite ligands and olefin dimerization 203
5.4.9 Use of the phosphonite functionality to synthesize other ligands 206
5.5 Experimental procedures for the syntheses of prototypical phosphinite and
phosphonite ligands 208
5.5.1 Phosphinite ligands 208
5.5.1.1 Me 2 P(OMe) 208
5.5.1.2 Et 2 POEt and EtP(OEt) 2 209
5.5.1.3 Synthesis of methyl 3,4-bis-O -[bis(3,5-dimethylphenyl)phosphino]-
2,6-di-O -benzoyl-a -D -glucopyranoside (Ligand 8) 209
5.5.1.4 Preparation of phenyl 2,3-bis-O -[bis[3,5-bis(trifluoromethyl)
phenyl]-phosphino)-4,6-O -benzylidene-glucopyranoside 211
5.5.1.5 Preparation of bis-(pentafluorophenyl)chlorophosphine 212
5.5.1.6 An alternate general procedure for phosphinite incorporation.
[(2S,3R)-3-phenylthio-4-methylpent-2-oxy]diphenylphosphine 212
5.5.1.7 Metal-template synthesis of an amino1,2-diarylphosphinediarylphophinite complex 213 5
5.5.1.8 Procedure for the preparation of a bis-aminodiaryphosphine (R)-37 213
5.5.1.9 (-)-(S)-4-tert -butyl-2-{1-di(2'-methylphenyl)phosphinite-
1-methyl-ethyl}-4,5-dihydro-oxazole 214
5.5.1.10 (R)-7-(2-phenyl-6,7-dihydro-5H-[1]pyrindin)-di-(2'-methylphenyl)-
phosphinite 215
5.5.2 Phosphonite ligands 217
5.5.2.1 (IR,7R)-9,9-dimethyl-2,2,4,6.6-penta(2-naphthyl)-3,5,8,l0-tetraoxa-
4-phosphabicyclo[5.3.0]-decane 217
5.5.2.2 (IR,7R)-9,9-dimethyl-2,2,4,6.6-penta(2-naphthyl)-3,5,8,l0-tetraoxa-
4-phosphabicyclo/5.3.0]-decane 218
5.5.2.3 Synthesis of (S)-2-[2-(diphenylphosphino)phenyl]-1,3,2-dinaphtho
[d1,2,f1,2]dioxaphosphe-pine 219
5.5.2.4 4,5-Bis{di[(2-tert-butyl)phenyl]phosphonito}-9,9-dimethylxanthene 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
6.2.1 P,N-ligands 235
6.2.1.1 Oxazoline-based P,N-ligands 235
6.2.1.2 Imidazoline-based P,N-ligands 243
6.2.1.3 Oxazole-, thiazole-, and imidazole-based
P,N-ligands 243
6.2.1.4 Pyridine-based P,N-ligands 245
6.2.1.5 Amine- and imine-based P,N-ligands 247
6.2.1.6 Other P,N-ligands 250
6.2.2 P,O-ligands 250
6.2.3 P,S-ligands 252
6.2.4 P,C-ligands 255
6.3 Conclusion 257
6.4 Experimental procedures 257
6.4.1 Synthesis of PHOX ligand 257
6.4.2 Synthesis of NeoPHOX ligand 259
References 260
7 Phospholes 267
Duncan Carmichael
7.1 Introduction 267
7.2 Creation of phospholes for use as ligands 269
7.2.1 Reactions of phosphorus dihalides with metallated dienes 269
7.2.2 Reactions of phosphorus dihalides with dienes 270
7.2.3 Michael addition of primary phosphines to dienes 271
7.3 Postsynthetic functionalisation 271
7.3.1 Functionalisation at phosphorus 271
7.3.2 Use of electrophiles 272
7.3.3 Use of nucleophiles and aromatics 272
7.3.4 Elaboration about the phosphole nucleus 272
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
8.2.1 Electronic properties 288
8.2.2 Structural characteristics and steric properties 289
8.2.3 Reactivity of phosphinines 290
8.3 Synthesis of Phosphinines 292
8.3.1 O + /P exchange reaction 292
8.3.2 Tin route 294
8.3.3 [4 + 2] cycloaddition reactions 294
8.3.4 Ring expansion methods 295
8.3.5 Metal-mediated functionalizations 296
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
9.6.1 Synthesis of BABAR-Phos 49a (R =i-Pr) 315
9.6.2 Synthesis of BABAR-Phos 49b (R = 3,5-(CF3)2C6H3) 316
References 317
10 Phosphaalkenes 321
Julien Dugal-Tessier, Eamonn D. Conrad, Gregory R. Dake, and Derek P. Gates
10.1 Introduction 321
10.1.1 Frontier molecular orbitals of phosphaalkenes 322
10.2 Synthesis of phosphaalkenes 324
10.2.1 Diphosphinidenecyclobutene (DPCB) synthesis (P,P chelates) 324
10.2.2 Bidentate-chelating P,P phosphaalkene ligands 325
10.2.3 Phosphaalkenes capable of P,N-chelation to metals 326
10.2.4 P,X achiral phosphaalkene ligands (X=P, O, S) 326
10.2.5 Synthesis of enantiomerically pure P,X ligands (X=P, N) 328
10.3 Catalysis with phosphaalkene ligands 329
10.3.1 Ethylene polymerization 329
10.3.2 Cross-coupling reactions 330
10.3.3 Hydro- and dehydrosilylation 332
10.3.4 Hydroamination and hydroamidation 333
10.3.5 Isomerization reactions 334
10.3.6 Allylic substitution 335
10.3.7 Asymmetric catalysis 336
10.4 Concluding remarks 337
10.5 Experimental procedures for representative ligands 338
10.5.1 Synthesis of DPCB 338
10.5.2 Synthesis of PhAkOx 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
11.3.1 Tris(trimethylsilyl)phosphine, P(SiMe 3 ) 3 345
11.3.2tert -butylphosphaalkene, Me 3 SiP = C(OSiMe 3 ) t Bu (systematic name
[2,2-dimethyl-1-(trimethylsiloxy)propylidene](trimethylsilyl) phosphine) 346
11.3.3 (2,2-dimethylpropylidyne)phosphine; t BuC=P 347
11.4 Adamanylphosphaalkyne, AdC=P 348
11.4.1 Adamant-1-yl(trimethylsiloxy)methylidene (trimethylsilyl) phosphane 348
11.4.2 (Adamant-1-ylmethylidyne)phosphane 348
11.5 Mesitylphosphaalkyne, MesC=P 349
11.5.1 Preparation of potassium bis(trimethylsilyl)phosphide {KP(SiMe 3 ) 2 } 349
11.5.2 Mesityl(trimethylsiloxy)methylene trimethylsilylphosphane 349
11.5.3 Mesitylphosphaalkyne 350
11.6 Phospholide anions 350
11.6.1 Preparation of Cp 2 Zr(PC t Bu) 2 351
11.6.2 Preparation of ClP(PC t Bu) 2 351
11.6.3 Preparation of the triphospholide anion and derivation to give the
triphenylstannylphosphole 352
11.6.4 Preparation of Cl 3 P 3 (C t Bu) 2 352
11.6.5 Preparation of the triphospholide anion 352
11.7 1,3,5-Triphosphabenzene 352
11.7.1 Preparation of Cl 3 VN t Bu 353
11.7.2 Preparation of 1,3,5-triphospabenzene; P 3 (C t Bu) 3 353
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
12.3.1 Synthesis starting from tricoordinated 1,3,2-oxazaphospholidines 363
12.3.2 Synthesis starting from tetracoordinated 1,3,2-oxazaphospholidines 364
12.3.3 Synthesis starting from 1,3,2-oxazaphospholidine borane complexes 366
12.3.3.1 Interest of the boranephosphorus complex chemistry 366
12.3.3.2 Ephedrine method 366
12.3.3.3 Methyl phosphinite boranes as P-chiral electrophilic building blocks 367
12.3.3.4 Chlorophosphine boranes as P-chiral electrophilic building blocks 368
12.3.3.5 Designing P-chiral aminophosphine phosphinites(AMPP*) 371
12.3.3.6 P-chiralo -hydroxyaryl phosphines 371
12.3.3.7 P-chiral secondary phosphine boranes 373
12.3.3.8 P-chiral 1,2-diphosphinobenzenes 373
12.3.3.9 Strategies for the enantiodivergent synthesis of P-chiral ligands 375
12.4 Designing of P-chiral ligands using amines as chiral auxiliaries 377
12.4.1 Sparteine as chiral auxiliary 377
12.4.2 a -Arylethylamines as chiral auxiliaries 381
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
13.3.1 Alkoxycarbonylation 395
13.3.2 Hydroformylation and hydrocyanation 397
13.3.3 Pd-catalysed coupling reactions 399
13.3.4 Asymmetric hydrogenation 400
13.4 Experimental procedures for phosphatrioxa-adamantanes ligands 401
13.4.1 Preparation of CgPH 401
13.4.2 Preparation of CgPH(BH 3 ) 402
13.4.3 Preparation of CgPBr 402
13.4.4 Preparation of CgPCH 2 CH 2 CH 2 PCg (L1) 402
13.4.5 Preparation of CgPPh (L7) 402
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
14.3.1 Phosphines and phosphinites 409
14.3.2 Phosphites and phosphonites 414
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
15.2.1 H bonding 429
15.2.2 Metal template assembly 440
15.2.3 Ion templation 445
15.3 Conclusions 446
15.4 Experimental procedures 447
15.4.1 General remarks 447
15.4.2 Synthesis of UREAPhos 447
15.4.3 Synthesis of METAMORPhos 448
15.4.4 Synthesis of supraphos 450
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
17.2.1 Solid-phase synthesis using phosphine-containing amino acids 481
17.2.1.1 Synthesis of phosphine-containing amino acids 482
17.2.1.2 Synthesis and application of phosphine-containing peptides 484
17.2.2 Functionalisation of peptides with phosphines 485
17.2.2.1 Phosphinomethylation of amines 485
17.2.2.2 Phosphine modification of peptides via imine or amide formation 485
17.3 Oligonucleotide-based phosphine ligands 487
17.3.1 Covalent anchoring of phosphines to DNA 487
17.4 Phosphine-based artificial metalloenzymes 488
17.4.1 Supramolecular anchoring of phosphines to proteins 489
17.4.1.1 Avidinbiotin 489
17.4.1.2 Antibodies 490
17.4.2 Covalent anchoring of phosphines 491
17.5 Conclusions and outlook 492
17.6 Representative synthetic procedures 493
17.6.1 Artificial hydrogenases based on the biotinstreptavidin technology 493
17.6.2 Site-selective covalent modification of proteins with phosphines
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
18.5.1 Biphasic systems based on CO2 516
18.6 Experimental section 518
18.6.1 Trisodium salt of 3,3,3-phosphinetriylbenzenesulfonic acid (TPPTS) 518
18.6.2 2,7-bis(SO3Na)-Xantphos 519
18.6.3 Sulfonated BINAP 519
18.6.4 Synthesis of Tris(1H,1H,2H,2H-perfluorooctyl)phosphine 520
18.6.5 Synthesis of Tris (4-tridecafluorohexylphenyl)phosphine 520
18.6.6 (Meta-sulfonatophenyl)diphenylphosphine, sodium salt (monosulfonated
triphenylphosphine, TPPMS) 522
18.6.7 1-Propyl-3-methylimidazolium diphenyl(3-sulfonatophenyl)-phosphine
([PrMIM][TPPMS]) 523
18.6.8 4,4-Phosphorylated 2,2-Bis(diphenylphosphanyl)-1,1-binaphthyl 523
18.6.9 Synthesis of (R)-6,6-bis(perfluorohexyl)-2,2
bis (diphenylphosphino)-1,1-binaphthyl ((R)-Rf-BINAP) 524
References 526
Index
