Phosphorus(III)Ligands in Homogeneous Catalysis

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 Phosphoramidite-phosphines 145

4.4.5.2 Phosphoramidite-phosphite 147

4.4.5.3 Phosphoramidite-amines 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 Phosphine-phosphinite and amine-phosphinite ligands 173

5.3.5 Phosphinites from amines, amino alcohols, and amino acids 174

5.3.5.1 Aminophosphines 174

5.3.5.2 Aminophosphine-phosphinite (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 Thioether-phosphinite ligands 182

5.3.9.2 Oxazoline-phosphinite and pyridine-phosphinite ligands 184

5.3.9.3 An alkene-phosphinite 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 Phosphine-phosphonite 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 Oxazoline-phosphonite 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 PhAk-Ox 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

11.3.2 tert -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 borane-phosphorus 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-chiral o -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 Avidin-biotin 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 biotin-streptavidin 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