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Ligand Design in Metal Chemistry
Reactivity and Catalysis
Mark Stradiotto (Edited by), M Stradiotto (Author), Rylan J. Lundgren (Edited by), Stephen L. Buchwald (Foreword by), David Milstein (Foreword by)
9781118839836, Wiley
Hardback, published 21 October 2016
448 pages
24.6 x 17.3 x 2.8 cm, 0.816 kg
"Catalysis underpins both modern industrial and academic chemistry, improving reaction sustainability, shaping reaction selectivity and facilitating fundamentally new reaction pathways. While the focus is often on the showpiece metals themselves, the ligands are the true shapers of this reactivity. Stradiotto and Lundgren have curated a collection that certainly celebrates ligands across a wide array of applications. At over 400 pages across 13 chapters written by world leaders in catalysis and ligand design, the book is a modern resource for those working in the area. The book opens with a chapter detailing the underlying key concepts that feature throughout the rest of the book. This is likely the only chapter which would serve the undergraduate student but as a stand-alone chapter would indeed provide a strong additional resource for final year students on a catalysis and/or coordination chemistry course. From there, each chapter captures a specific vignette of relevance to the authors. The overall book is by no means comprehensive in coverage, but it neither intends to be or indeed should be. Instead, it permits the reader to learn about specific topics in the key authors voice, and from a unified perspective of the ligand design... The book, as a secondary impact, also helps to showcase the important contribution Canadian researchers have made to catalysis and ligand design, with 6 of the 13 chapters written by authors at Canadian universities. In closing, the collection of articles found in Ligand Design in Metal Chemistry is certainly worthy of a book shelf spot for those working in the field of ligand design in catalysis. As the content of the book is necessarily focussed, this reviewer recommends a thorough read through the table of contents to ensure that chapters of particular interest are complemented by those that will introduce the reader to new areas." (AOC, Feb 2017)
The design of ancillary ligands used to modify the structural and reactivity properties of metal complexes has evolved into a rapidly expanding sub-discipline in inorganic and organometallic chemistry. Ancillary ligand design has figured directly in the discovery of new bonding motifs and stoichiometric reactivity, as well as in the development of new catalytic protocols that have had widespread positive impact on chemical synthesis on benchtop and industrial scales. Ligand Design in Metal Chemistry presents a collection of cutting-edge contributions from leaders in the field of ligand design, encompassing a broad spectrum of ancillary ligand classes and reactivity applications. Topics covered include: This book will be a valuable reference for academic researchers and industry practitioners working in the field of ligand design, as well as those who work in the many areas in which the impact of ancillary ligand design has proven significant, for example synthetic organic chemistry, catalysis, medicinal chemistry, polymer science and materials chemistry.
List of Contributors xii Foreword by Stephen L. Buchwald xiv Foreword by David Milstein xvi Preface xvii 1 Key Concepts in Ligand Design: An Introduction 1 1.1 Introduction 1 1.2 Covalent bond classification and elementary bonding concepts 2 1.3 Reactive versus ancillary ligands 4 1.4 Strong© and weak©field ligands 4 1.5 Trans effect 6 1.6 Tolman electronic parameter 6 1.7 Pearson acid base concept 8 1.8 Multidenticity, ligand bite angle, and hemilability 8 1.9 Quantifying ligand steric properties 10 1.10 Cooperative and redox non©innocent ligands 12 1.11 Conclusion 12 References 13 2 Catalyst Structure and Cis–Trans Selectivity in Ruthenium©ased Olefin Metathesis 15 2.1 Introduction 15 2.2 Metathesis reactions and mechanism 17 2.2.1 Types of metathesis reactions 17 2.2.2 Mechanism of Ru©catalyzed olefin metathesis 19 2.2.3 Metallacycle geometry 19 2.2.4 Influencing syn–anti preference of metallacycles 22 2.3 Catalyst structure and E/Z selectivity 24 2.3.1 Trends in key catalysts 24 2.3.2 Catalysts with unsymmetrical NHCs 26 2.3.3 Catalysts with alternative NHC ligands 29 2.3.4 Variation of the anionic ligands 31 2.4 Z©selective Ru©ased metathesis catalysts 33 2.4.1 Thiophenolate©ased Z©selective catalysts 33 2.4.2 Dithiolate©ased Z©selective catalysts 34 2.5 Cyclometallated Z©selective metathesis catalysts 36 2.5.1 Initial discovery 36 2.5.2 Model for selectivity 37 2.5.3 Variation of the anionic ligand 38 2.5.4 Variation of the aryl group 40 2.5.5 Variation of the cyclometallated NHC substituent 41 2.5.6 Reactivity of cyclometallated Z©selective catalysts 42 2.6 Conclusions and future outlook 42 References 43 3 Ligands for Iridium©catalyzed Asymmetric Hydrogenation of Challenging Substrates 46 3.1 Asymmetric hydrogenation 46 3.2 Iridium catalysts based on heterobidentate ligands 49 3.3 Mechanistic studies and derivation of a model for the enantioselective step 57 3.4 Conclusion 63 References 64 4 Spiro Ligands for Asymmetric Catalysis 66 4.1 Development of chiral spiro ligands 66 4.2 Asymmetric hydrogenation 73 4.2.1 Rh©catalyzed hydrogenation of enamides 73 4.2.2 Rh© or Ir©catalyzed hydrogenation of enamines 73 4.2.3 Ir©catalyzed hydrogenation of α,β©unsaturated carboxylic acids 75 4.2.4 Ir©catalyzed hydrogenation of olefins directed by the carboxy group 78 4.2.5 Ir©catalyzed hydrogenation of conjugate ketones 79 4.2.6 Ir©catalyzed hydrogenation of ketones 80 4.2.7 Ru©catalyzed hydrogenation of racemic 2©substituted aldehydes via dynamic kinetic resolution 81 4.2.8 Ru©catalyzed hydrogenation of racemic 2©substituted ketones via DKR 82 4.2.9 Ir©catalyzed hydrogenation of imines 84 4.3 Carbon–carbon bond©forming reactions 85 4.3.1 Ni©catalyzed hydrovinylation of olefins 85 4.3.2 Rh©catalyzed hydroacylation 85 4.3.3 Rh©catalyzed arylation of carbonyl compounds and imines 86 4.3.4 Pd©catalyzed umpolung allylation reactions of aldehydes, ketones, and imines 87 4.3.5 Ni©catalyzed three©component coupling reaction 87 4.3.6 Au©catalyzed Mannich reactions of azlactones 89 4.3.7 Rh©catalyzed hydrosilylation/cyclization reaction 89 4.3.8 Au©catalyzed [2 + 2] cycloaddition 90 4.3.9 Au©catalyzed cyclopropanation 91 4.3.10 Pd©catalyzed Heck reactions 91 4.4 Carbon–heteroatom bond©forming reactions 91 4.4.1 Cu©catalyzed N©¤H bond insertion reactions 91 4.4.2 Cu©, Fe©, or Pd©catalzyed O©¤H insertion reactions 93 4.4.3 Cu©catalyzed S©¤H, Si©¤H and B©¤H insertion reactions 95 4.4.4 Pd©catalyzed allylic amination 95 4.4.5 Pd©catalyzed allylic cyclization reactions with allenes 97 4.4.6 Pd©catalyzed alkene carboamination reactions 98 4.5 Conclusion 98 References 98 5 Application of Sterically Demanding Phosphine Ligands in Palladium©Catalyzed Cross©Coupling leading to C(sp2)©¤E Bond Formation (E = NH2 , OH, and F) 104 5.1 Introduction 104 5.1.1 General mechanistic overview and ancillary ligand design considerations 105 5.1.2 Reactivity challenges 107 5.2 Palladium©catalyzed selective monoarylation of ammonia 108 5.2.1 Initial development 109 5.2.2 Applications in heterocycle synthesis 110 5.2.3 Application of Buchwald palladacycles and imidazole©derived monophosphines 112 5.2.4 Heterobidentate κ2©P,N ligands: chemoselectivity and room temperature reactions 115 5.2.5 Summary 117 5.3 Palladium©catalyzed selective hydroxylation of (hetero)aryl halides 117 5.3.1 Initial development 118 5.3.2 Application of alternative ligand classes 120 5.3.3 Summary 122 5.4 Palladium©catalyzed nucleophilic fluorination of (hetero)aryl (pseudo)halides 123 5.4.1 Development of palladium©catalyzed C(sp2)©¤F coupling employing (hetero)aryl triflates 124 5.4.2 Discovery of biaryl monophosphine ancillary ligand modification 125 5.4.3 Extending reactivity to (hetero)aryl bromides and iodides 127 5.4.4 Summary 128 5.5 Conclusions and outlook 129 Acknowledgments 130 References 131 6 Pd©N©Heterocyclic Carbene Complexes in Cross©Coupling Applications 134 6.1 Introduction 134 6.2 N©heterocyclic carbenes as ligands for catalysis 135 6.3 The relationship between N©heterocyclic carbene structure and reactivity 136 6.3.1 Steric parameters of NHC ligands 136 6.3.2 Electronic parameters of NHC ligands 138 6.3.3 Tuning the electronic properties of NHC ligands 139 6.4 Cross©coupling reactions leading to C©¤C bonds that proceed through transmetalation 140 6.5 Kumada–Tamao–Corriu 141 6.6 Suzuki–Miyaura 148 6.6.1 The formation of tetra©ortho©substituted (hetero)biaryl compounds 149 6.6.2 Enantioselective Suzuki–Miyaura coupling 153 6.6.3 Formation of sp3©¤sp3 or sp2 ©¤sp3 bonds 156 6.6.4 The formation of (poly)heteroaryl compounds 158 6.7 Negishi coupling 163 6.7.1 Mechanistic studies: investigating the role of additives and the nature of the active transmetalating species 166 6.7.2 Selective cross©coupling of secondary organozinc reagents 168 6.8 Conclusion 170 References 171 7 Redox Non©innocent Ligands: Reactivity and Catalysis 176 7.1 Introduction 176 7.2 Strategy I. Redox non©innocent ligands used to modify the Lewis acid–base properties of the metal 179 7.3 Strategy II. Redox non©innocent ligands as electron reservoirs 181 7.4 Strategy III. Cooperative ligand©centered reactivity based on redox active ligands 192 7.5 Strategy IV. Cooperative substrate©centered radical© ype reactivity based on redox non©innocent substrates 195 7.6 Conclusion 200 References 201 8 Ligands for Iron©ased Homogeneous Catalysts for the Asymmetric Hydrogenation of Ketones and Imines 205 8.1 Introduction: from ligands for ruthenium to ligands for iron 205 8.1.1 Ligand design elements in precious metal homogeneous catalysts for asymmetric direct hydrogenation and asymmetric transfer hydrogenation 205 8.1.2 Effective ligands for iron©catalyzed ketone and imine reduction 212 8.1.3 Ligand design elements for iron catalysts 213 8.2 First generation iron catalysts with symmetrical [6.5.6]©P©N©N©P ligands 216 8.2.1 Synthetic routes to ADH and ATH iron catalysts 217 8.2.2 Catalyst properties and mechanism of reaction 218 8.3 Second generation iron catalysts with symmetrical [5.5.5]©P©N©N©P ligands 220 8.3.1 Synthesis of second generation ATH catalysts 220 8.3.2 Asymmetric transfer hydrogenation catalytic properties and mechanism 222 8.3.3 Substrate scope 226 8.4 Third generation iron catalysts with unsymmetrical [5.5.5]©P©NH©N©Pʹ ligands 227 8.4.1 Synthesis of bis(tridentate)iron complexes and P©NH©NH2 ligands 227 8.4.2 Template©assisted synthesis of iron P©NH©N©Pʹ complexes 228 8.4.3 Selected catalytic properties 229 8.4.4 Mechanism 230 8.5 Conclusions 231 Acknowledgments 232 References 232 9 Ambiphilic Ligands: Unusual Coordination and Reactivity Arising from Lewis Acid Moieties 237 9.1 Introduction 237 9.2 Design and structure of ambiphilic ligands 238 9.3 Coordination of ambiphilic ligands 242 9.3.1 Complexes featuring a pendant Lewis acid 242 9.3.2 Bridging coordination involving M → Lewis acid interactions 243 9.3.3 Bridging coordination of M©¤X bonds 248 9.3.4 Ionization of M©¤X bonds 250 9.4 Reactivity of metallic complexes deriving from ambiphilic ligands 251 9.4.1 Lewis acid enhancement effect in Si©¤Si and C©¤C coupling reactions 251 9.4.2 Hydrogenation, hydrogen transfer and hydrosilylation reactions assisted by boranes 255 9.4.3 Activation/functionalization of N2 and CO 262 9.5 Conclusions and outlook 264 References 266 10 Ligand Design in Enantioselective Ring©opening Polymerization of Lactide 270 10.1 Introduction 270 10.1.1 Tacticity in PLA 271 10.1.2 Metal catalysts for the ROP of lactide 272 10.1.3 Ligand design in the enantioselective polymerization of racemic lactide 274 10.2 Indium and zinc complexes bearing chiral diaminophenolate ligands 292 10.2.1 Zinc catalysts supported by chiral diaminophenolate ligands 292 10.2.2 The first indium catalyst for lactide polymerization 294 10.2.3 Polymerization of cyclic esters with first generation catalyst 295 10.2.4 Ligand modifications 296 10.3 Dinuclear indium complexes bearing chiral salen© ype ligands 297 10.3.1 Chiral indium salen complexes 297 10.3.2 Polymerization studies 297 10.4 Conclusions and future directions 301 References 302 11 Modern Applications of Trispyrazolylborate Ligands in Coinage Metal Catalysis 308 11.1 Introduction 308 11.2 Trispyrazolylborate ligands: main features 310 11.3 Catalytic Systems Based on TpXMl Complexes (M = Cu, Ag) 311 11.3.1 Carbene addition reactions 312 11.3.2 Carbene insertion reactions 314 11.3.3 Nitrene addition reactions 319 11.3.4 Nitrene insertion reactions 321 11.3.5 Oxo transfer reactions 322 11.3.6 Atom transfer radical reactions 324 11.4 Conclusions 326 Acknowledgments 326 References 327 12 Ligand Design in Modern Lanthanide Chemistry 330 12.1 Introduction and scope of the review 330 12.2 C©donor ligands 333 12.2.1 Silylalkyls 333 12.2.2 Terphenyls 335 12.2.3 Substituted cyclopentadienyls 336 12.2.4 Constrained geometry cyclopentadienyls 338 12.2.5 Benzene complexes 340 12.2.6 Zerovalent arenes 342 12.2.7 Tethered N©heterocyclic carbenes 343 12.3 N©donor ligands 344 12.3.1 Hexamethyldisilazide 344 12.3.2 Substituted trispyrazolylborates 347 12.3.3 Silyl©substituted triamidoamine, [N(CH2Ch2NSiMe2But)3]3– 348 12.3.4 NacNac, {N(Dipp)C(Me)CHC(Me)N(Dipp)}− 349 12.4 P©donor ligands 349 12.4.1 Phospholides 349 12.5 Multiple bonds 350 12.5.1 Ln¨TCR2 350 12.6 Conclusions 356 Notes 357 References 357 13 Tight Bite Angle N,O©Chelates. Amidates, Ureates and Beyond 364 13.1 Introduction 364 13.2 Applications in reactivity and catalysis 377 13.3 Conclusions 400 References 401
Rylan J. Lundgren and Mark Stradiotto
Brendan L. Quigley and Robert H. Grubbs
Marc©André Müller and Andreas Pfaltz
Shou©Fei Zhu and Qi©Lin Zhou
Mark Stradiotto and Rylan J. Lundgren
Jennifer Lyn Farmer, Matthew Pompeo, and Michael G. Organ
Bas de Bruin, Pauline Gualco, and Nanda D. Paul
Demyan E. Prokopchuk, Samantha A. M. Smith, and Robert H. Morris
Ghenwa Bouhadir and Didier Bourissou
Kimberly M. Osten, Dinesh C. Aluthge, and Parisa Mehrkhodavandi
Ana Caballero, M. Mar Díaz©Requejo, Manuel R. Fructos, Juan Urbano, and Pedro J. Pérez
David P. Mills and Stephen T. Liddle
12.5.2 Ln ¨T NR 354
12.5.3 Ln ¨T O 355
Scott A. Ryken, Philippa R. Payne, and Laurel L. Schafer
13.1.1 N,O©Proligands 366
13.1.2 Preparing metal complexes 367
13.2.1 Polymerizations 377
13.2.2 Hydrofunctionalization 385
Index 406
Subject Areas: Chemistry [PN]
