Filling the gap for an up-to-date reference that presents the field of organophosphorus chemistry in a comprehensive and clearly structured way, this one-stop source covers the chemistry, properties, and applications from life science and medicine. Divided into two parts, the first presents the chemistry of various phosphorus-containing compounds and their synthesis, including ylides, acids, and heterocycles. The second part then goes on to look at applications in life science and bioorganic chemistry. Last but not least, such important practical aspects as 31P-NMR and protecting strategies for these compounds are presented.
For organic, bioinorganic, and medicinal chemists, as well as those working on organometallics, and for materials scientists. The book, a contributed work, features a team of renowned scientists from around the world whose expertise spans the many aspects of modern organophosphorus chemistry.
Table of Contents
1 Phosphines and Related Tervalent Phosphorus Systems 1
Piet W. N. M. van Leeuwen
1.1 Introduction 1
1.2 Synthesis of Phosphorus Ligands 3
1.3 Ligand Properties 18
1.4 Rhodium-Catalyzed Hydroformylation with Xantphos-Type Ligands 29
1.5 Cross-Coupling Catalysis with Mono- and Bidentate Phosphines 33
2 Recent Developments in Phosphonium Chemistry 59
Mathieu Berchel and Paul-Alain Jaffrès
2.1 Introduction 59
2.2 Synthesis of Phosphonium Salts 60
2.3 Phosphonium Salts as a Tool for Organic Synthesis 70
2.4 Phosphonium Salts for Biological and Medical Applications 84
2.5 Conclusion 102
3 Phosphorus Ylides and Related Compounds 113
Alejandro Presa Soto and Joaquín García-Álvarez
3.1 Introduction 113
3.2 Preparation of Phosphorus Ylides 115
3.3 Applications of Phosphorus Ylides in Organic Synthesis 130
3.4 Conclusions 148
Acknowledgments 148
References 148
4 Low-Coordinate Phosphorus Compounds with Phosphaorganic Multiple Bond Systems 163
Dietrich Gudat
4.1 Introduction 163
4.2 General Considerations on Structure and Bonding of PC Multiple Bond Systems 165
4.3 Synthetic Approaches 171
4.4 Reactivity 177
4.5 Applications of Phosphorus-Carbon Multiple Bond Systems 184
References 209
5 Pentacoordinate Phosphorus Compounds 219
Masaaki Yoshifuji
5.1 History of Pentacoordinate Phosphorus Compounds 219
5.2 Preparation of Pentacoordinate Phosphorus Compounds 221
5.3 Structure of Trigonal Bipyramid and Square Pyramid 228
5.4 Interconversion of Pentacoordinate Phosphorus Compounds 229
5.5 Apicophilicity 232
5.6 Hydrolysis of Phosphate Esters 233
References 235
6 Hexacoordinate Phosphorus Compounds 239
Masaaki Yoshifuji
6.1 Preparation and Structure of Hexacoordinate Phosphorus Compounds 239
6.2 Stereochemistry of Hexacoordinate Phosphorus Compounds 241
6.3 Hexacoordinate Compounds with Intramolecular Coordination 242
6.4 Theoretical Studies on Hexacoordinate Phosphorus Compounds 245
6.5 Hexacoordinate Phosphates as Counter Anions for Complex Ligands 245
References 247
7 Methods for the Introduction of the Phosphonate Moiety into Complex Organic Molecules 249
Wouter Debrouwer, IrisWauters, and Christian V. Stevens
7.1 Introduction 250
7.2 P - C (sp3) Bond Formation 252
7.3 P - C (sp2) Bond Formation 261
7.4 P - C (sp) Bond Formation 278
7.5 Conclusion 285
References 286
8 Phosphorus Heterocycles 295
Viktor Iaroshenko and SatenikMkrtchyan
8.1 Introduction 295
8.2 Five-Membered Phosphorus Heterocycles 296
8.3 Five-Membered Phosphorus Heterocycles with One Phosphorus Atom: 1H-Phospholes and Fused Aromatic Systems Containing Phosphole Ring 296
8.4 Aromaticity of 1H-Phospholes and 1H-Phosphole-Containing Heterocyclic Systems 303
8.6 Synthesis of 1H-Phospholes Following [4+1] and [2+2+1] Synthetic Strategies 307
8.7 Synthesis of Phospholes by [3+2] Cyclization Reaction 312
8.8 Synthesis of 1H-Phospholes by Intramolecular Cyclization Reactions 312
8.9 Synthesis of Phosphorus-Containing Porphyrin Hybrids 316
8.10 Fused Heterocycles with 1H-Phosphole Structural Fragment 317
8.11 Synthesis-Fused 1H-Phospholes Following [4+1] and [2+2+1] Synthetic Strategies 320
8.12 Synthesis of Fused Phospholes Following [3+2] Synthetic Strategies 324
8.13 Synthesis of Fused Phospholes Following Intramolecular Cyclization Strategies 329
8.14 Application of C - H Bond Activation Protocols for the Synthesis of Benzo[b]phosphindoles via Intramolecular Cyclization 339
8.15 Synthesis of π-Conjugated Benzo[b]phosphindoles Following [2+2+2] Cycloaddition Synthetic Strategy 341
8.16 Five-Membered Phosphorus Heterocycles with One Heteroatom 342
8.17 Synthesis of 1,2- and 1,3-Heterophospholes: General Overview 345
8.18 1,2-Azaphospholes 347
8.19 Synthesis of 1,2-Azaphospholes Following [3+2] Synthetic Strategies 351
8.20 Synthesis of Fused 1,2-Azaphospholes via Intramolecular Cyclization Strategy 353
8.21 Synthesis of 1,2-Oxophospholes, 1,2-Thiaphosphols, and 1,2-Selenophosphols 356
8.23 Synthesis of 1,3-Azaphospholes by Intramolecular Cyclization Reactions 362
8.24 Synthesis of 1,3-Oxaphospholes, 1,3-Thiaphospholes, and 1,3-Selenophospholes 365
8.25 Six-Membered Phosphorus Heterocycles 372
8.26 Phosphinines: General Overview 372
8.27 Synthesis of λ3- and λ5-Phosphenines: General Overview 376
8.28 Synthesis of Phosphenines Following [5+1] Synthetic Strategy 378
8.29 Synthesis of Phosphenines Following [4+2] Synthetic Strategy 381
8.30 Synthesis of Phosphenines from Phospholes 388
8.31 Synthesis of Phosphenines Following 1,6-Electrocyclization Strategy 393
8.32 Synthesis of Fused λ3- and λ5-Phosphenines: General Overview 396
8.33 Synthesis of Fused Phosphenines Following [4+2] Synthetic Strategy 397
8.34 Synthesis of Fused Phosphenines by Intramolecular Cyclization 400
8.35 Synthesis of Fused Phosphenines Following [5+1] Synthetic Strategy 401
8.36 Six-Membered Phosphorus Heterocycles with One Heteroatom 404
8.37 Synthesis 1,2-, 1,3-, and 1,4-Heterophosphinines 408
8.38 1,2-Azaphosphenines 408
8.39 Synthesis of 1,2-Azaphosphenines Following [3+1+1+1] Synthetic Strategy 409
8.40 Synthesis of 1,2-Azaphosphenines Following [3+3] Synthetic Strategy 414
8.41 Synthesis of 1,2-Azaphosphenines Following [3+2+1] Synthetic Strategies 414
8.42 Synthesis of 1,2-Azaphosphenines Following [5+1] Synthetic Strategies 414
8.43 Synthesis of 1,2-Azaphosphenines Following [4+2] Synthetic Strategies 415
8.44 Synthesis of 1,2-Azaphosphenines Following Intramolecular Cyclization Strategies 417
8.45 1,3-Azaphosphenines 419
8.46 Synthesis of 1,3-Azaphosphenines Following [5+1] Synthetic Strategy 419
8.47 Synthesis of 1,3-Azaphosphenines Following [4+2] Synthetic Strategies 419
8.48 1,4-Azaphosphenines 421
8.49 Oxygen- and Sulfur-Containing Heterophosphinines 424
8.50 Application and Synthesis of Phosphoborine Systems 429
8.51 Application and Synthesis of 1,4-Phosphasiline System 432
8.52 Synthesis of Germanium- and Tin-Containing Heterophosphinines 437
References 441
9 Modern Aspects of 31P NMR Spectroscopy 457
David S. Glueck
9.1 Introduction 457
9.2 Chemical Shifts 459
9.3 Coupling Constants 464
9.4 Two-Dimensional (2D) 31P NMR Techniques 469
9.5 Analytical Methods 471
9.6 Diffusion-Ordered NMR Spectroscopy (DOSY) 476
9.7 Solid-State (SS) 31P NMR 479
9.8 Physical and Chemical Processes of Organophosphorus Compounds 483
9.9 Identification of Intermediates and Monitoring Their Reactivity 488
9.10 Conclusion 490
Acknowledgment 490
References 490
10 Phosphorus in Chemical Biology and Medicinal Chemistry 499
Marlon Vincent V. Duro, Dana Mustafa, Boris A. Kashemirov, and Charles E.McKenna
10.1 Phosphorus and Life: An Introduction 499
10.2 Unnatural Nucleotides as Chemical Tools in Biology 500
10.3 Prodrugs of Nucleoside Phosphates and Phosphonates 516
10.4 Synthesis and Medical Applications of Bisphosphonates 522
10.5 Conclusion: The Future of Phosphorus in Chemical Biology and Medicinal Chemistry 531
References 531
11 Future Trends in Organophosphorus Chemistry 545
Shin-ichi Kawaguchi and Akiya Ogawa
11.1 Introduction 545
11.2 Facile C - P Bond Formation Methods 545
11.3 Utilization of Organophosphorus Compounds 551
References 553
Index 557
