Ligand Design in Metal 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
Rylan J. Lundgren and Mark Stradiotto
 
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?-based Olefin Metathesis 15
Brendan L. Quigley and Robert H. Grubbs
 
2.1 Introduction 15
 
2.2 Metathesis reactions and mechanism 17
 
2.3 Catalyst structure and E/Z selectivity 24
 
2.4 Z?-selective Ru?-based metathesis catalysts 33
 
2.5 Cyclometallated Z?-selective metathesis catalysts 36
 
2.6 Conclusions and future outlook 42
 
References 43
 
3 Ligands for Iridium?-catalyzed Asymmetric Hydrogenation of Challenging Substrates 46
Marc?-André Müller and Andreas Pfaltz
 
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
Shou?-Fei Zhu and Qi?-Lin Zhou
 
4.1 Development of chiral spiro ligands 66
 
4.2 Asymmetric hydrogenation 73
 
4.3 Carbon-carbon bond?-forming reactions 85
 
4.4 Carbon-heteroatom bond?-forming reactions 91
 
4.5 Conclusion 98
 
References 98
 
5 Application of

Mark Stradiotto, Department of Chemistry, Dalhousie University, Canada
Rylan Lundgren, Department of Chemistry, University of Alberta, Canada
Both professors have a well-established track-record of working in the field of organometallic ligand design and catalysis, and have published extensively on the subjects of metal-catalyzed cross-coupling, novel transition-metal bond activation, and asymmetric catalysis. They are co-inventors of the now commercialized DalPhos ligand family and have broad experience of the field of ligand design. Professor Stradiotto has worked in the field of organometallic chemistry for the past fourteen years. Professor Lundgren earned his PhD under the supervision of Prof Stradiotto at Dalhousie University in 2010. Following a PDF at MIT and Caltech with Prof. Greg Fu, Rylan accepted a faculty position at the University of Alberta (Canada).

"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)