Again, this is contextualized though reference to the early work of Williard, but then shifts to modern lithium amide chemistry capable of being done under aerobic conditions. Most particularly, though, modern diffusion methods have allowed us to better understand the real solution chemistries of heterobimetallic formulations. This has been greatly enabled by the work of Stalke, raising the bar where the accuracy of molecular weight determination in solution is concerned. In consequence, diffusion analysis and multinuclear spectroscopy has prompted a much truer understanding of the aggregation and solvation of highly applied systems—for example the turbo reagents of Knochel.
The final set of chapters deal with up‐to‐date aspects of (mostly main group) synthetic applications of organometallic and metalloorganic chemistry. Chapter 7 is focused on the chemistry of boryl anions. In these, the nucleophilicity at the group 13 centre contrasts with the more common Lewis acid chemistry of boron, enabling a range of boryl‐substituted organic, main group, and organometallic compounds to be prepared. Chapter 8 deals very much with synthetic organic chemistry as accessed by ate complexes. A range of ate complexes are discussed, but the chapter opens, appropriately enough, with work done in Sendai in the early 1990s. Initial discussion of sterically demanding tetramethylzincate in a range of transformations eventually shifts to the advent of organoamidozincates that are structurally covered in earlier chapters. From there, the evolution of aluminate and cyanocuprate congeners follows naturally. Again, structural aspects of these species feature elsewhere, but the discussion here focuses on their potential in aromatic derivatization. The chapter also continues a theme from the previous one. Efforts to exert control over the reactivity of boryl anions through ate complexes are presented in the context of novel nucleophilic boration. Lastly, Chapter 9 finishes the book as it started, looking at organocopper compounds. Copper‐mediated processes are well established, prompting much organocopper structural chemistry. Whereas efforts have often focused on alkynyl‐ and arylorganocopper complexes, the emphasis here is instead on traditionally unstable mono‐alkenyl and butadienylcopper compounds. The potential of steric, coordinative and synergistic strategies for preventing decomposition are examined.
Overall, this book seeks to bring the reader up‐to‐date with developments in the field of modern polar organometallic chemistry, particularly in the context of the emergent areas of synergic and cooperative species. The recent advances in our understanding of the operation of these systems are presented, but the evolution of the area is described, offering a context and explaining the need and rationale for the advent of new reagents. The hope is that this is done in a way that makes the text accessible to students as well as academics and industrial scientists, arming them with a broad understanding of how these systems present new opportunities to the synthetic chemist.
A. E. H. Wheatley Cambridge, UK
M. Uchiyama Tokyo, Japan
List of Contributors
Alistair M. Broughton Yusuf Hamied Department of Chemistry University of Cambridge Cambridge, UK
Andrew E. H. Wheatley Yusuf Hamied Department of Chemistry University of Cambridge Cambridge, UK
Andrew J. Peel Yusuf Hamied Department of Chemistry University of Cambridge Cambridge, UK
Andrew S. S. Wilson Department of Chemistry University of Bath Claverton Down, UK
Anne‐Frédérique Pécharman Department of Chemistry University of Bath Claverton Down, UK
Antoine Buchard Department of Chemistry University of Bath Claverton Down, UK
Chao Wang Graduate School of Pharmaceutical Sciences The University of Tokyo Tokyo, Japan
Eva Hevia Department für Chemie, Biochemie und Pharmazie Universität Bern Bern, Switzerland
Frances N. Singer Department of Chemistry University of Bath Claverton Down, UK
Keiichi Hirano Graduate School of Pharmaceutical Sciences The University of Tokyo Tokyo, Japan
Leonie J. Bole Department für Chemie, Biochemie und Pharmazie Universität Bern Bern, Switzerland
Liang Liu College of Chemistry Peking University Beijing, China
Makoto Yamashita Department of Molecular and Macromolecular Chemistry Graduate School of Engineering Nagoya University Nagoya, Japan
Mamta Bhandari Department of Chemical Sciences Indian Institute of Science Education and Research Mohali India
Masanobu Uchiyama Graduate School of Pharmaceutical Sciences The University of Tokyo Tokyo, Japan
Research Initiative for Supra‐Materials (RISM)
Shinshu University
Nagano, Japan
Masanori Shigeno Graduate School of Pharmaceutical Sciences Tohoku University Sendai, Japan
Michael S. Hill Department of Chemistry University of Bath Claverton Down, UK
Robert E. Mulvey WestCHEM, Department of Pure and Applied Chemistry University of Strathclyde Glasgow, UK
Sandeep Rawat Department of Chemical Sciences Indian Institute of Science Education and Research Mohali India
Sanjay Singh Department of Chemical Sciences Indian Institute of Science Education and Research Mohali India
Sharanappa Nembenna School of Chemical Sciences National Institute of Science Education and Research Bhubaneswar India
Stuart D. Robertson WestCHEM, Department of Pure and Applied Chemistry University of Strathclyde Glasgow, UK
Yoshinori Kondo Graduate School of Pharmaceutical Sciences Tohoku University Sendai, Japan
Zhenfeng Xi College of Chemistry Peking University Beijing, China
Acknowledgements
The editors wish to thank John Wiley & Sons for the opportunity to publish this work. Our sincere thanks go to Sarah Higginbotham for proposing and supporting the idea of a book covering the recent advances in the field of polar organometallics. We are also grateful to Emma Strickland and the handling editors, particularly Katrina Maceda, for their constant support and advice. Finally, we would thank the chapter authors for contributing their expertise and time, without which this book could not have happened.
1 The Road to Aromatic Functionalization by Mixed‐metal Ate Chemistry
Masanori Shigenoa, Andrew J. Peelb, Andrew E. H. Wheatleyb, and Yoshinori Kondoa
a Graduate School of Pharmaceutical Sciences, Tohoku University, Sendai, Japan
