N-HETEROCYCLIC CARBENES IN SYNTHESIS

This first handbook to focus solely on the application of N-heterocyclic carbenes in synthesis covers metathesis, organocatalysis, oxidation and asymmetric reactions, along with experimental procedures. Written by leading international experts this is a valuable and practical source for every organic chemist.

Steven P. Nolan was born in Quebec City, Canada. He received his B.Sc. in chemistry from the University of West Florida and his Ph.D. from the University of Miami where he worked under the supervision of Professor Carl D. Hoff. After a postdoctoral stay with Professor Tobin J. Marks at Northwestern University, he joined the Department of Chemistry of the University of New Orleans in 1990. He now holds the rank of University Research Professor of Chemistry. His research interests include organometallic chemistry, homogeneous catalysis and most recently the use of N-heterocyclic carbenes in homogeneous catalysis.

Preface.
List of Contributors.
1 N-Heterocyclic Carbene–Ruthenium Complexes in Olefin Metathesis (Samuel Beligny and Siegfried Blechert).
1.1 Introduction.
1.2 N-Heterocyclic Carbene–Ruthenium Complexes.
1.3 Second-generation NHC-Ru Catalysts.
1.4 Enantioselective Ruthenium Olefin Catalysts.
1.5 Solid Supported NHC-Ru Complexes.
1.6 Conclusion and Outlook.
References.
2 Ruthenium N-Heterocyclic Carbene Complexes in Organic Transformations (Excluding Metathesis) (Suzanne Burling, Belinda M. Paine, and Michael K. Whittlesey).
2.1 Introduction.
2.2 Hydrogenation and Hydrosilylation Reactions.
2.3 Isomerization.
2.4 Other Reactivity.
2.5 Tandem Reactions [29].
2.6 Conclusions.
References.
3 Cross-coupling Reactions Catalyzed by Palladium N-Heterocyclic Carbene Complexes (Natalie M. Scott and Steven P. Nolan).
3.1 Introduction.
3.2 Palladium(0) NHC Complexes.
3.3 Palladium(ii) N-Heterocyclic Carbene Complexes.
3.4 Palladium/NHC Complexes as Catalysts.
3.5 Conclusion.
References.
4 Pd-NHC Complexes as Catalysts in Telomerization and Aryl Amination Reactions (David J. Nielsen and Kingsley J. Cavell).
4.1 Introduction.
4.2 Telomerization.
4.3 Buchwald–HartwigAmination Reactions Catalyzed by Pd(NHC) Complexes.
4.4 Conclusions.
References.
5 Metal-mediated and -catalyzed Oxidations Using N-Heterocyclic Carbene Ligands (Mitchell J. Schultz and MatthewS. Sigman).
5.1 Introduction.
5.2 Metal–NHC-mediated Activation of Molecular Oxygen.
5.3 Metal-catalyzed Oxidations, Pd.
5.4 Ir-catalyzed Oppenauer Oxidation of Alcohols.
5.5 Conclusion.
References.
6 Efficient and Selective Hydrosilylation of Alkenes and Alkynes Catalyzed by Novel N-Heterocyclic Carbene Pt⁰ Complexes (Guillaume Berthon-Gelloz and István E. Markó).
6.1 Introduction.
6.2 Initial Results.
6.3 Synthesis, Structure and Reactivity of (NHC)Pt(dvtms) Complexes.
6.4 Kinetic and Mechanistic Studies.
6.5 Hydrosilylation of Alkynes.
6.6 Summary.
References.
7 Ni-NHC Mediated Catalysis (Janis Louie).
7.1 Introduction.
7.2 Rearrangement Reactions.
7.3 Cycloaddition Reactions.
7.4 Reductive Coupling Reactions.
7.5 Oligomerization and Polymerization.
7.6 Hydrogenation.
7.7 Conclusions.
References.
8 Asymmetric Catalysis with Metal N-Heterocyclic Carbene Complexes (Marc Mauduit and Hervé Clavier).
8.1 Introduction.
8.2 Concept, Design and Synthesis of Chiral NHC Complexes.
8.3 Asymmetric Hydrogenation.
8.4 Asymmetric 1,4-Addition.
8.5 Asymmetric 1,2-Addition.
8.6 Asymmetric Hydrosilylation.
8.7 Asymmetric Olefin Metathesis.
8.8 Allylic Substitution Reaction.
8.9 Asymmetric a-Arylation.
8.10 Palladium-catalyzed Kinetic Resolution.
8.11 Conclusion and Outlook.
References.
9 Chelate and Pincer Carbene Complexes (Guillermina Rivera and Robert H. Crabtree).
9.1 Introduction.
9.2 Design Strategy.
9.3 Synthetic Strategies.
9.4 Failure to Chelate.
9.5 Ligand Properties.
9.6 Catalysis.
9.7 Conclusions.
References.
10 The Quest for Longevity and Stability of Iridium-based Hydrogenation Catalysts: N-Heterocyclic Carbenes and Crabtree’s Catalyst (Leslie D. Vazquez-Serrano and Jillian M. Buriak).
10.1 Introduction: Rhodium and Iridium-based Hydrogenation Catalysts.
10.2 Buildingupon Crabtree’s Catalyst with N-Heterocyclic Carbenes.
10.3 Chiral Iridium N-Heterocyclic Catalysts.
10.4 Conclusions.
References.
11 Cu-, Ag-, and Au-NHC Complexes in Catalysis (Pedro J. Pérez and M. Mar Díaz-Requejo).
11.1 Introduction.
11.2 Copper.
11.3 Silver.
11.4 Gold.
11.5 Cu-, Ag-, and Au-NHC Complexes as Catalysts for Carbene Transfer Reactions from Ethyl Diazoacetate.
References.
12 N-Heterocyclic Carbenes as Organic Catalysts (AndrewP. Dove, Russell C. Pratt, Bas G. G. Lohmeijer, Hongbo Li, Erik C. Hagberg, Robert M. Waymouth, and James L. Hedrick).
12.1 Introduction.
12.2 In situ Generation of Free Carbenes.
12.3 Small Molecule Transformations.
12.4 Living Ring-opening Polymerization.
References.
Subject Index.