Phosphorus(III)Ligands in Homogeneous Catalysis Design and Synthesis

by Kamer, Paul C. J.; van Leeuwen, Piet W. N. M.

• ISBN13: 9780470666272
• ISBN10: 0470666277
• Edition: 1st
• Format: Hardcover
• Copyright: 2012-06-25
• Publisher: Wiley

Summary

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.

Author Biography

Paul C.J. Kamer, EaStCHEM, School of Chemistry, University of St. Andrews, Scotland.

Piet W.N.M. van Leeuwen, Institute of Chemical Research of Catalonia (ICIQ), Tarragona, Spain.

Table of Contents

List of Contributors	p. xv
Preface	p. xix
Phosphorus Ligand Effects in Homogeneous Catalysis and Rational Catalyst Design	p. 1
Introduction	p. 1
Properties of phosphorus ligands	p. 7
Electronic ligand parameters	p. 7
Steric ligand parameters	p. 9
Bite angle effects	p. 10
Electronic bite angle effect	p. 11
Steric bite angle effect	p. 12
Steric versus electronic bite angle effects	p. 12
Molecular electrostatic potential (MESP) approach	p. 13
Asymmetric ligands	p. 15
Rational ligand design in nickel-catalysed hydrocyanation	p. 19
Introduction	p. 19
Mechanistic insights	p. 20
Rational design	p. 20
Conclusions	p. 22
References	p. 23
Chiral Phosphines and Diphosphines	p. 27
Introduction	p. 27
Early developments	p. 27
Chiral chelating diphosphines with a linking scaffold	p. 30
Building chiral backbones from naturally available materials	p. 30
Early development	p. 30
Syntheses of DIOP variants	p. 31
Synthesis from other natural chiral backbones	p. 33
Design and synthesis of chiral backbones	p. 35
Chiral backbones synthesized through asymmetric catalysis	p. 35
Design and synthesis of ligands containing spiro backbones	p. 37
Design and synthesis of chiral ferrocene backbones	p. 40
Design and synthesis of other chiral backbones	p. 41
Synthesis from optical resolution of phosphine precursors or intermediates	p. 43
Chiral atropisomeric biaryl diphosphines	p. 46
Synthesis of BINAP and its derivatives	p. 46
Synthesis of atropisomeric biaryl ligands	p. 49
General strategies of synthesizing of atropisomeric biaryl ligands	p. 52
Chiral phosphacyclic diphosphines	p. 52
Fundamental discovery and syntheses of BPE and DuPhos	p. 52
Design and synthesis of bisphosphetanes	p. 56
Design and synthesis of bisphospholanes	p. 58
BPE and DuPhos analogue ligands	p. 58
P-stereogenic bisphospholane ligands	p. 60
Design and synthesis of bisphospholes	p. 63
Design and synthesis of bisphosphinanes	p. 65
Design and synthesis of bisphosphepines	p. 66
Summary of synthetic strategies of phosphacycles	p. 68
P-stereogenic diphosphine ligands	p. 68
Experimental procedures for the syntheses of selected diphosphine ligands	p. 69
Synthesis procedure for DIOP* ligand	p. 69
Synthesis procedure of SDP ligands	p. 70
Synthesis procedure of ( R , R )-BICP	p. 71
Synthesis procedure of SEGPHOS	p. 71
Synthesis procedure of Ph-BPE	p. 72
Synthesis procedure of TangPhos	p. 73
Synthesis procedure of Binaphane	p. 74
Concluding remarks	p. 75
References	p. 75
Design and Synthesis of Phosphite Ligands for Homogeneous Catalysis	p. 81
Introduction	p. 81
Synthesis of phosphites	p. 82
Monophosphites	p. 82
Symmetrically substituted monophosphites	p. 82
Nonsymmetrically substituted monophosphites	p. 83
Caged monophosphites	p. 84
Monophosphites bearing dioxaphospho-cyclic units	p. 84
Diphosphite ligands	p. 94
Diphosphites not containing a dioxaphospho-cyclic unit	p. 94
Diphosphites bearing dioxaphospho-cyclic units	p. 95
Triphosphites	p. 105
Highlights of catalytic applications of phosphite ligands	p. 106
Hydrogenation reactions	p. 106
Functionalization of alkenes: hydroformylation and hydrocyanation	p. 108
Hydroformylation	p. 108
Hydrocyanation	p. 110
Addition of nucleophiles to carbonyl compounds and derivatives	p. 110
1,2-addition	p. 111
1,4-addition	p. 111
Allylic substitution reactions	p. 113
Miscellaneous reactions	p. 117
General synthetic procedures	p. 122
Symmetrically substituted phosphites	p. 122
Nonsymmetrically substituted phosphites	p. 123
Phosphites bearing dioxaphospho-cyclic units	p. 123
References	p. 124
Phosphoramidite Ligands	p. 133
Introduction	p. 133
History	p. 134
Synthesis of phosphoramidites	p. 134
Reactivity of the phosphoramidites	p. 135
Types of phosphoramidite ligands	p. 136
Acyclic monodentate phosphoramidites	p. 136
Cyclic monodentate phosphoramidites based on diols	p. 136
Synthesis of binaphthol- and biphenol-based phosphoramidites	p. 137
Synthesis of TADDOL-based phosphoramidites	p. 140
Synthesis of spiro-based phosphoramidites	p. 141
Synthesis of 1,2-diol-based phosphoramidites	p. 141
Phosphoramidites based on unusual diols	p. 141
Cyclic phosphoramidites based on amino alcohols	p. 142
Bis-phosphoramidites	p. 143
Bis-phosphoramidites based on diamines	p. 143
Bis-phosphoramidites based on diols	p. 144
Other bidentate phosphoramidites	p. 145
Mixed bidentate ligands	p. 145
Phosphoramidite-phosphines	p. 145
Phosphoramidite-phosphite	p. 147
Phosphoramidite-amines	p. 148
Other bidentate phosphoramidite ligands	p. 149
Polydendate phosphoramidites	p. 149
Conclusion	p. 153
Synthetic procedures	p. 153
References	p. 153
Phosphinite and Phosphonite Ligands	p. 159
Introduction	p. 159
General methods for synthesis of complexes	p. 160
Syntheses and applications of phosphinite ligands	p. 162
Early studies	p. 162
Phosphinite ligands from carbohydrates	p. 163
Rh-catalyzed asymmetric hydrogenation of dehydroaminoacids	p. 164
Ni(0)-catalyzed asymmetric hydrocyanation	p. 166
Ni(0)- and Pd(0)-catalyzed allylic substitution by carbon nucleophiles	p. 170
Rh(I)-catalyzed hydroformylation of vinylarenes	p. 171
Ni(II)-catalyzed asymmetric hydrovinylation of alkenes	p. 171
Ligands for homogeneous catalysis in water	p. 172
Phosphinite ligands from other alcohols	p. 172
Phosphine-phosphinite and amine-phosphinite ligands	p. 173
Phosphinites from amines, amino alcohols, and amino acids	p. 174
Aminophosphines	p. 174
Aminophosphine-phosphinite (AMPP) ligands	p. 176
Bisphosphinite ligands with other scaffoldings	p. 179
1,1'-Diaryl-2,2'-phosphinites and dynamic conformational control in asymmetric catalysis	p. 180
Monophosphinite ligands	p. 182
Hybrid ligands containing phosphinites	p. 182
Thioether-phosphinite ligands	p. 182
Oxazoline-phosphinite and pyridine-phosphinite ligands	p. 184
An alkene-phosphinite ligand	p. 186
Chiral transition metal Lewis acids bearing electron-withdrawing phosphinites	p. 187
Synthesis and applications of phosphonite ligands	p. 188
Early studies	p. 188
Phosphonites from TADDOL and related compounds	p. 189
Phosphonites derived from 2,2'-hydroxybiaryls and related compounds	p. 193
Phosphine-phosphonite ligands	p. 196
Phosphonites with paracyclophane backbone	p. 196
Phosphonites with a spirobisindane backbone	p. 197
Miscellaneous phosphonite ligands	p. 198
Development of phosphonite ligands for industrially relevant processes	p. 199
Phosphonite ligands in hydroformylation	p. 199
Phosphonite ligands in Ni(0)-catalyzed hydrocyanation	p. 201
Oxazoline-phosphonite ligands and olefin dimerization	p. 203
Use of the phosphonite functionality to synthesize other ligands	p. 206
Experimental procedures for the syntheses of prototypical phosphinite and phosphonite ligands	p. 208
Phosphinite ligands	p. 208
Me 2 P(OMe)	p. 208
Et 2 POEt and EtP(OEt) 2	p. 209
Synthesis of methyl 3,4-bis- O -[bis(3,5-dimethylphenyl)phosphino]- 2,6-di- O -benzoyl- a - D -glucopyranoside (Ligand 8)	p. 209
Preparation of phenyl 2,3-bis- O -[bis[3,5-bis(trifluoromethyl) phenyl]-phosphino)-4,6- O -benzylidene-glucopyranoside	p. 211
Preparation of bis-(pentafluorophenyl)chlorophosphine	p. 212
An alternate general procedure for phosphinite incorporation. [(2S,3R)-3-phenylthio-4-methylpent-2-oxy]diphenylphosphine	p. 212
Metal-template synthesis of an amino1,2-diarylphosphinediarylphophinite complex	p. 213
Procedure for the preparation of a bis-aminodiaryphosphine (R)-37	p. 213
(-)-(S)-4- tert -butyl-2-{1-di(2'-methylphenyl)phosphinite- 1-methyl-ethyl}-4,5-dihydro-oxazole	p. 214
(R)-7-(2-phenyl-6,7-dihydro-5H-[1]pyrindin)-di-(2'-methylphenyl)- phosphinite	p. 215
Phosphonite ligands	p. 217
(IR,7R)-9,9-dimethyl-2,2,4,6.6-penta(2-naphthyl)-3,5,8,l0-tetraoxa- 4-phosphabicyclo[5.3.0]-decane	p. 217
(IR,7R)-9,9-dimethyl-2,2,4,6.6-penta(2-naphthyl)-3,5,8,l0-tetraoxa- 4-phosphabicyclo/5.3.0]-decane	p. 218
Synthesis of (S)-2-[2-(diphenylphosphino)phenyl]-1,3,2-dinaphtho [d1,2,f1,2]dioxaphosphe-pine	p. 219
4,5-Bis{di[(2-tert-butyl)phenyl]phosphonito}-9,9-dimethylxanthene	p. 219
Acknowledgments	p. 221
Abbreviations	p. 221
References	p. 222
Mixed Donor Ligands	p. 233
Introduction: general design principles	p. 233
Synthesis of bidentate P,X-ligands	p. 235
P,N-ligands	p. 235
Oxazoline-based P,N-ligands	p. 235
Imidazoline-based P,N-ligands	p. 243
Oxazole-, thiazole-, and imidazole-based P,N-ligands	p. 243
Pyridine-based P,N-ligands	p. 245
Amine- and imine-based P,N-ligands	p. 247
Other P,N-ligands	p. 250
P,O-ligands	p. 250
P,S-ligands	p. 252
P,C-ligands	p. 255
Conclusion	p. 257
Experimental procedures	p. 257
Synthesis of PHOX ligand	p. 257
Synthesis of NeoPHOX ligand	p. 259
References	p. 260
Phospholes	p. 267
Introduction	p. 267
Creation of phospholes for use as ligands	p. 269
Reactions of phosphorus dihalides with metallated dienes	p. 269
Reactions of phosphorus dihalides with dienes	p. 270
Michael addition of primary phosphines to dienes	p. 271
Postsynthetic functionalisation	p. 271
Functionalisation at phosphorus	p. 271
Use of electrophiles	p. 272
Use of nucleophiles and aromatics	p. 272
Elaboration about the phosphole nucleus	p. 272
Phosphole coordination chemistry	p. 273
Phospholes in catalysis	p. 276
Experimental procedures	p. 279
References	p. 280
Phosphinine Ligands	p. 287
Introduction	p. 287
Ligand properties	p. 288
Electronic properties	p. 288
Structural characteristics and steric properties	p. 289
Reactivity of phosphinines	p. 290
Synthesis of Phosphinines	p. 292
O + /P exchange reaction	p. 292
Tin route	p. 294
[4 + 2] cycloaddition reactions	p. 294
Ring expansion methods	p. 295
Metal-mediated functionalizations	p. 296
Coordination chemistry	p. 297
Reactivity of transition metal complexes	p. 300
Application of phosphinines in homogeneous catalysis	p. 300
Experimental procedure for the synthesis of selected phosphinines	p. 303
References	p. 305
Highly Strained Organophosphorus Compounds	p. 309
Introduction	p. 309
Three-membered rings	p. 310
Rearrangements	p. 312
Homogeneous catalysis	p. 313
Conclusions	p. 314
Experimental procedures	p. 315
Synthesis of BABAR-Phos 49a (R = i-Pr)	p. 315
Synthesis of BABAR-Phos 49b (R = 3,5-(CF3)2C6H3)	p. 316
References	p. 317
Phosphaalkenes	p. 321
Introduction	p. 321
Frontier molecular orbitals of phosphaalkenes	p. 322
Synthesis of phosphaalkenes	p. 324
Diphosphinidenecyclobutene (DPCB) synthesis (P,P chelates)	p. 324
Bidentate-chelating P,P phosphaalkene ligands	p. 325
Phosphaalkenes capable of P,N-chelation to metals	p. 326
P,X achiral phosphaalkene ligands (X=P, O, S)	p. 326
Synthesis of enantiomerically pure P,X ligands (X=P, N)	p. 328
Catalysis with phosphaalkene ligands	p. 329
Ethylene polymerization	p. 329
Cross-coupling reactions	p. 330
Hydro- and dehydrosilylation	p. 332
Hydroamination and hydroamidation	p. 333
Isomerization reactions	p. 334
Allylic substitution	p. 335
Asymmetric catalysis	p. 336
Concluding remarks	p. 337
Experimental procedures for representative ligands	p. 338
Synthesis of DPCB	p. 338
Synthesis of PhAk-Ox	p. 338
Acknowledgments	p. 339
References	p. 339
Phosphaalkynes	p. 343
Introduction	p. 343
General experimental	p. 344
Preparation of PC t Bu	p. 344
Tris(trimethylsilyl)phosphine, P(SiMe 3 ) 3	p. 345
tert -butylphosphaalkene, Me 3 SiP = C(OSiMe 3 ) t Bu (systematic name [2,2-dimethyl-1-(trimethylsiloxy)propylidene]-(trimethylsilyl) phosphine)	p. 346
(2,2-dimethylpropylidyne)phosphine; t BuC=P	p. 347
Adamanylphosphaalkyne, AdC=P	p. 348
Adamant-1-yl(trimethylsiloxy)methylidene (trimethylsilyl) phosphane	p. 348
(Adamant-1-ylmethylidyne)phosphane	p. 348
Mesitylphosphaalkyne, MesC=P	p. 349
Preparation of potassium bis(trimethylsilyl)phosphide {KP(SiMe 3 ) 2 }	p. 349
Mesityl(trimethylsiloxy)methylene trimethylsilylphosphane	p. 349
Mesitylphosphaalkyne	p. 350
Phospholide anions	p. 350
Preparation of Cp 2 Zr(PC t Bu) 2	p. 351
Preparation of ClP(PC t Bu) 2	p. 351
Preparation of the triphospholide anion and derivation to give the triphenylstannylphosphole	p. 352
Preparation of Cl 3 P 3 (C t Bu) 2	p. 352
Preparation of the triphospholide anion	p. 352
1,3,5-Triphosphabenzene	p. 352
Preparation of Cl 3 VN t Bu	p. 353
Preparation of 1,3,5-triphospabenzene; P 3 (C t Bu) 3	p. 353
References	p. 353
P-chiral Ligands	p. 355
Introduction	p. 355
Designing P-chiral ligands using alcohols as chiral auxiliaries	p. 357
Designing P-chiral ligands using amino alcohols as chiral auxiliaries	p. 363
Synthesis starting from tricoordinated 1,3,2-oxazaphospholidines	p. 363
Synthesis starting from tetracoordinated 1,3,2-oxazaphospholidines	p. 364
Synthesis starting from 1,3,2-oxazaphospholidine borane complexes	p. 366
Interest of the borane-phosphorus complex chemistry	p. 366
Ephedrine method	p. 366
Methyl phosphinite boranes as P-chiral electrophilic building blocks	p. 367
Chlorophosphine boranes as P-chiral electrophilic building blocks	p. 368
Designing P-chiral aminophosphine phosphinites (AMPP*)	p. 371
P-chiral o -hydroxyaryl phosphines	p. 371
P-chiral secondary phosphine boranes	p. 373
P-chiral 1,2-diphosphinobenzenes	p. 373
Strategies for the enantiodivergent synthesis of P-chiral ligands	p. 375
Designing of P-chiral ligands using amines as chiral auxiliaries	p. 377
Sparteine as chiral auxiliary	p. 377
a -Arylethylamines as chiral auxiliaries	p. 381
Conclusion	p. 381
Experimental procedures	p. 383
References	p. 385
Phosphatrioxa-Adamantane Ligands	p. 391
Introduction	p. 391
Synthesis of phosphatrioxa-adamantanes	p. 393
Catalysis supported by phosphatrioxa-adamantane ligands	p. 395
Alkoxycarbonylation	p. 395
Hydroformylation and hydrocyanation	p. 397
Pd-catalysed coupling reactions	p. 399
Asymmetric hydrogenation	p. 400
Experimental procedures for phosphatrioxa-adamantanes ligands	p. 401
Preparation of CgPH	p. 401
Preparation of CgPH(BH 3 )	p. 402
Preparation of CgPBr	p. 402
Preparation of CgPCH 2 CH 2 CH 2 PCg (L1)	p. 402
Preparation of CgPPh (L7)	p. 402
References	p. 402
Calixarene-based Phosphorus Ligands	p. 405
Introduction	p. 405
Conformational properties	p. 407
Calixarene-based phosphorus ligands	p. 409
Phosphines and phosphinites	p. 409
Phosphites and phosphonites	p. 414
Applications in homogeneous catalysis	p. 422
Experimental procedures	p. 424
References	p. 425
Supramolecular Bidentate Phosphorus Ligands	p. 427
Introduction: general design principles	p. 427
Construction of bidentate phosphorus ligands via self-assembly	p. 429
H bonding	p. 429
Metal template assembly	p. 440
Ion templation	p. 445
Conclusions	p. 446
Experimental procedures	p. 447
General remarks	p. 447
Synthesis of UREAPhos	p. 447
Synthesis of METAMORPhos	p. 448
Synthesis of supraphos	p. 450
References	p. 459
Solid-phase Synthesis of Ligands	p. 463
Introduction	p. 463
Insoluble supports in ligand synthesis	p. 466
Soluble polymeric supports	p. 470
Supported ligands in catalysis	p. 472
Solid-phase synthesis of nonsupported ligands	p. 473
Conclusions and outlook	p. 475
Experimental procedures	p. 476
References	p. 478
Biological Approaches	p. 481
Introduction	p. 481
Peptide-based phosphine ligands	p. 481
Solid-phase synthesis using phosphine-containing amino acids	p. 481
Synthesis of phosphine-containing amino acids	p. 482
Synthesis and application of phosphine-containing peptides	p. 484
Functionalisation of peptides with phosphines	p. 485
Phosphinomethylation of amines	p. 485
Phosphine modification of peptides via imine or amide formation	p. 485
Oligonucleotide-based phosphine ligands	p. 487
Covalent anchoring of phosphines to DNA	p. 487
Phosphine-based artificial metalloenzymes	p. 488
Supramolecular anchoring of phosphines to proteins	p. 489
Avidin-biotin	p. 489
Antibodies	p. 490
Covalent anchoring of phosphines	p. 491
Conclusions and outlook	p. 492
Representative synthetic procedures	p. 493
Artificial hydrogenases based on the biotin-streptavidin technology	p. 493
Site-selective covalent modification of proteins with phosphines via hydrazone linkage	p. 494
Acknowledgments	p. 495
References	p. 495
The Design of Ligand Systems for Immobilisation in Novel Reaction Media	p. 497
Introduction	p. 497
Aqueous biphasic catalysis	p. 499
Fluorous biphasic catalysis	p. 503
Ionic liquids as reaction media	p. 507
Supercritical fluids as solvents in single- and multiphasic reaction systems	p. 512
Biphasic systems based on CO2	p. 516
Experimental section	p. 518
Trisodium salt of 3,3′,3″-phosphinetriylbenzenesulfonic acid (TPPTS)	p. 518
2,7-bis(SO3Na)-Xantphos	p. 519
Sulfonated BINAP	p. 519
Synthesis of Tris(1H,1H,2H,2H-perfluorooctyl)phosphine	p. 520
Synthesis of Tris (4-tridecafluorohexylphenyl)phosphine	p. 520
(Meta-sulfonatophenyl)diphenylphosphine, sodium salt (monosulfonated triphenylphosphine, TPPMS)	p. 522
1-Propyl-3-methylimidazolium diphenyl(3-sulfonatophenyl)-phosphine ([PrMIM][TPPMS])	p. 523
4,4′-Phosphorylated 2,2′-Bis(diphenylphosphanyl)-1,1′-binaphthyl	p. 523
Synthesis of (R)-6,6′-bis(perfluorohexyl)-2,2′ bis (diphenylphosphino)-1,1′-binaphthyl ((R)-Rf-BINAP)	p. 524
References	p. 526
Index
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