Organophosphorus Chemistry

Viktor O. Iaroshenko was born in 1980 in Kiev, Ukraine. He received his MS in chemistry (2003) and PhD in organic chemistry (2009) from Kyiv National Taras Shevchenko University (Ukraine) under the supervision of Prof. Dr. Sci. Andrey A. Tolmachev. 2009-2013 he was a group leader (assistant professor) at the Chemistry Institute, University of Rostock, Germany. 2013-2014 he was a visiting research assistant professor at University of Illinois at Chicago, Chicago, USA. Presently he is a Principle Investigator and a head of Laboratory of Homogeneous Catalysis and Molecular Design at Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Poland. His scientific interests include drug discovery, application of fluorine and phosphorus chemistry in molecular and drug design, combinatorial chemistry, chemistry of heterocyclic compounds, element organic chemistry and green chemistry. He is co-author of more than 75 papers. He is also recipient of several grants from Polish National Science Centre (NCN).

• 1 Phosphines and Related Tervalent Phosphorus Systems 1Piet W. N. M. van Leeuwen1.1 Introduction 11.2 Synthesis of Phosphorus Ligands 31.3 Ligand Properties 181.4 Rhodium-Catalyzed Hydroformylation with Xantphos-Type Ligands 291.5 Cross-Coupling Catalysis with Mono- and Bidentate Phosphines 332 Recent Developments in Phosphonium Chemistry 59Mathieu Berchel and Paul-Alain Jaffrès2.1 Introduction 592.2 Synthesis of Phosphonium Salts 602.3 Phosphonium Salts as a Tool for Organic Synthesis 702.4 Phosphonium Salts for Biological and Medical Applications 842.5 Conclusion 1023 Phosphorus Ylides and Related Compounds 113Alejandro Presa Soto and Joaquín García-Álvarez3.1 Introduction 1133.2 Preparation of Phosphorus Ylides 1153.3 Applications of Phosphorus Ylides in Organic Synthesis 1303.4 Conclusions 148Acknowledgments 148References 1484 Low-Coordinate Phosphorus Compounds with Phosphaorganic Multiple Bond Systems 163Dietrich Gudat4.1 Introduction 1634.2 General Considerations on Structure and Bonding of PC Multiple Bond Systems 1654.3 Synthetic Approaches 1714.4 Reactivity 1774.5 Applications of Phosphorus–Carbon Multiple Bond Systems 184References 2095 Pentacoordinate Phosphorus Compounds 219Masaaki Yoshifuji5.1 History of Pentacoordinate Phosphorus Compounds 2195.2 Preparation of Pentacoordinate Phosphorus Compounds 2215.3 Structure of Trigonal Bipyramid and Square Pyramid 2285.4 Interconversion of Pentacoordinate Phosphorus Compounds 2295.5 Apicophilicity 2325.6 Hydrolysis of Phosphate Esters 233References 2356 Hexacoordinate Phosphorus Compounds 239Masaaki Yoshifuji6.1 Preparation and Structure of Hexacoordinate Phosphorus Compounds 2396.2 Stereochemistry of Hexacoordinate Phosphorus Compounds 2416.3 Hexacoordinate Compounds with Intramolecular Coordination 2426.4 Theoretical Studies on Hexacoordinate Phosphorus Compounds 2456.5 Hexacoordinate Phosphates as Counter Anions for Complex Ligands 245References 2477 Methods for the Introduction of the Phosphonate Moiety into Complex Organic Molecules 249Wouter Debrouwer, IrisWauters, and Christian V. Stevens7.1 Introduction 2507.2 P—C (sp3) Bond Formation 2527.3 P—C (sp2) Bond Formation 2617.4 P—C (sp) Bond Formation 2787.5 Conclusion 285References 2868 Phosphorus Heterocycles 295Viktor Iaroshenko and SatenikMkrtchyan8.1 Introduction 2958.2 Five-Membered Phosphorus Heterocycles 2968.3 Five-Membered Phosphorus Heterocycles with One Phosphorus Atom: 1H-Phospholes and Fused Aromatic Systems Containing Phosphole Ring 2968.4 Aromaticity of 1H-Phospholes and 1H-Phosphole-Containing Heterocyclic Systems 3038.6 Synthesis of 1H-Phospholes Following [4+1] and [2+2+1] Synthetic Strategies 3078.7 Synthesis of Phospholes by [3+2] Cyclization Reaction 3128.8 Synthesis of 1H-Phospholes by Intramolecular Cyclization Reactions 3128.9 Synthesis of Phosphorus-Containing Porphyrin Hybrids 3168.10 Fused Heterocycles with 1H-Phosphole Structural Fragment 3178.11 Synthesis-Fused 1H-Phospholes Following [4+1] and [2+2+1] Synthetic Strategies 3208.12 Synthesis of Fused Phospholes Following [3+2] Synthetic Strategies 3248.13 Synthesis of Fused Phospholes Following Intramolecular Cyclization Strategies 3298.14 Application of C—H Bond Activation Protocols for the Synthesis of Benzo[b]phosphindoles via Intramolecular Cyclization 3398.15 Synthesis of π-Conjugated Benzo[b]phosphindoles Following [2+2+2] Cycloaddition Synthetic Strategy 3418.16 Five-Membered Phosphorus Heterocycles with One Heteroatom 3428.17 Synthesis of 1,2- and 1,3-Heterophospholes: General Overview 3458.18 1,2-Azaphospholes 3478.19 Synthesis of 1,2-Azaphospholes Following [3+2] Synthetic Strategies 3518.20 Synthesis of Fused 1,2-Azaphospholes via Intramolecular Cyclization Strategy 3538.21 Synthesis of 1,2-Oxophospholes, 1,2-Thiaphosphols, and 1,2-Selenophosphols 3568.23 Synthesis of 1,3-Azaphospholes by Intramolecular Cyclization Reactions 3628.24 Synthesis of 1,3-Oxaphospholes, 1,3-Thiaphospholes, and 1,3-Selenophospholes 3658.25 Six-Membered Phosphorus Heterocycles 3728.26 Phosphinines: General Overview 3728.27 Synthesis of λ3- and λ5-Phosphenines: General Overview 3768.28 Synthesis of Phosphenines Following [5+1] Synthetic Strategy 3788.29 Synthesis of Phosphenines Following [4+2] Synthetic Strategy 3818.30 Synthesis of Phosphenines from Phospholes 3888.31 Synthesis of Phosphenines Following 1,6-Electrocyclization Strategy 3938.32 Synthesis of Fused λ3- and λ5-Phosphenines: General Overview 3968.33 Synthesis of Fused Phosphenines Following [4+2] Synthetic Strategy 3978.34 Synthesis of Fused Phosphenines by Intramolecular Cyclization 4008.35 Synthesis of Fused Phosphenines Following [5+1] Synthetic Strategy 4018.36 Six-Membered Phosphorus Heterocycles with One Heteroatom 4048.37 Synthesis 1,2-, 1,3-, and 1,4-Heterophosphinines 4088.38 1,2-Azaphosphenines 4088.39 Synthesis of 1,2-Azaphosphenines Following [3+1+1+1] Synthetic Strategy 4098.40 Synthesis of 1,2-Azaphosphenines Following [3+3] Synthetic Strategy 4148.41 Synthesis of 1,2-Azaphosphenines Following [3+2+1] Synthetic Strategies 4148.42 Synthesis of 1,2-Azaphosphenines Following [5+1] Synthetic Strategies 4148.43 Synthesis of 1,2-Azaphosphenines Following [4+2] Synthetic Strategies 4158.44 Synthesis of 1,2-Azaphosphenines Following Intramolecular Cyclization Strategies 4178.45 1,3-Azaphosphenines 4198.46 Synthesis of 1,3-Azaphosphenines Following [5+1] Synthetic Strategy 4198.47 Synthesis of 1,3-Azaphosphenines Following [4+2] Synthetic Strategies 4198.48 1,4-Azaphosphenines 4218.49 Oxygen- and Sulfur-Containing Heterophosphinines 4248.50 Application and Synthesis of Phosphoborine Systems 4298.51 Application and Synthesis of 1,4-Phosphasiline System 4328.52 Synthesis of Germanium- and Tin-Containing Heterophosphinines 437References 4419 Modern Aspects of 31P NMR Spectroscopy 457David S. Glueck9.1 Introduction 4579.2 Chemical Shifts 4599.3 Coupling Constants 4649.4 Two-Dimensional (2D) 31P NMR Techniques 4699.5 Analytical Methods 4719.6 Diffusion-Ordered NMR Spectroscopy (DOSY) 4769.7 Solid-State (SS) 31P NMR 4799.8 Physical and Chemical Processes of Organophosphorus Compounds 4839.9 Identification of Intermediates and Monitoring Their Reactivity 4889.10 Conclusion 490Acknowledgment 490References 49010 Phosphorus in Chemical Biology and Medicinal Chemistry 499Marlon Vincent V. Duro, Dana Mustafa, Boris A. Kashemirov, and Charles E.McKenna10.1 Phosphorus and Life: An Introduction 49910.2 Unnatural Nucleotides as Chemical Tools in Biology 50010.3 Prodrugs of Nucleoside Phosphates and Phosphonates 51610.4 Synthesis and Medical Applications of Bisphosphonates 52210.5 Conclusion: The Future of Phosphorus in Chemical Biology and Medicinal Chemistry 531References 53111 Future Trends in Organophosphorus Chemistry 545Shin-ichi Kawaguchi and Akiya Ogawa11.1 Introduction 54511.2 Facile C—P Bond Formation Methods 54511.3 Utilization of Organophosphorus Compounds 551References 553Index 557