Innovative catalysis in organic synthesis: oxidation, hydrogenation, and C-X bond forming reactions

Authored by a European team of leaders in the field, this book compiles innovative approaches for C-X bond forming processes frequently applied in organic synthesis. It covers all key types of catalysis, including homogeneous, heterogeneous, and organocatalysis, as well as mechanistic and computational studies. Special attention is focused on the improvement of efficiency and sustainability of important catalytic processes, such as selective oxidations, hydrogenation and cross-coupling reactions.The result is a valuable resource for both advanced researchers in academia and industry, as well as graduate students in organic chemistry aiming for chemo-, regio- or stereoselective synthesis of organic compounds using novel catalytic systems. INDICE: Foreword XIList of Contributors XIIIPart I Oxidation Reactions 11 Polyoxometalates as Homogeneous Oxidation Catalysts 3Mauro Carraro, Andrea Sartorel, Masooma Ibrahim, Nadeen Nsouli, Claire Jahier, Sylvain Nlate, Ulrich Kortz, and Marcella Bonchio1.1 Soluble Metal Oxides as Oxidation Catalysts 31.2 Homogeneous Oxidations with POMs Based Only on Mo(VI), W(VI), V(V) Addenda Ions 61.2.1 Oxidation with Hydrogen Peroxide by Peroxopolyoxotungstates-Dendrimers 81.2.2 Homogeneous Oxidation with Hydrogen Peroxide in the Presence of Vacant and Hybrid POMs 101.3 Homogeneous Oxidations with TMS-POMs 121.3.1 Peroxopolyoxometalates of Hf/Zr 131.3.2 Aerobic Oxidations with Polyoxopalladates 161.3.3 TMSPs as Oxygen-Evolving Catalysts 171.4 Conclusions 19Acknowledgments 19References 202 Bioinspired Oxidations Catalyzed by Nonheme Iron and Manganese Complexes 27Isaac Garcia-Bosch, Irene Prat, Xavi Ribas, and Miquel Costas2.1 Introduction 272.2 Catalytic Oxidation of C=C Bonds by Nonheme Iron and ManganeseComplexes 272.2.1 Epoxidation 272.2.1.1 Iron-Based Catalysts 272.2.1.2 Manganese-Based Catalysts 302.2.2 cis-Dihydroxylation 342.2.2.1 Iron-Based Catalysts342.2.2.2 Manganese-Based Catalysts 372.3 Catalytic Oxidation of C-H Bonds byNonheme Iron and Manganese Complexes 382.3.1 Hydroxylation 382.3.1.1 Iron-Based Catalysts 382.3.1.2 Manganese-Based Catalysts 402.3.2 Desaturation 412.3.2.1 Iron-Based Catalysts 412.3.2.2 Manganese-Based Catalysts 42References 433 The Fabulous Destiny of Sulfenic Acids 47Maria Chiara Aversa, Paola Bonaccorsi, David Madec, Guillaume Prestat, and Giovanni Poli3.1 Introduction 473.2 Synthesis of Stable Sulfenic Acids 483.3 Generation of Transient Sulfenic Acids 523.4 Reactivity of Sulfenic Acids in the Preparation of Sulfoxides and Unsymmetrical Disulfides 573.5 Synthesis of Stable Sulfenate Anions 623.6 Generation of Transient Sulfenate Anions Leading to Sulfoxides 653.7 Conclusions 73References 734 Sustainable Catalytic Oxidations with Peroxides 77Isabel W.C.E. Arends, Valeria Conte, and Giulia Licini4.1 Introduction 774.2 Metal-Based Selective Oxidations 784.2.1 Bromination Reactions 784.2.2 Oxidation of Nitrogen-Containing Substrates 854.2.3 Oxidation of Sulfur-Containing Substrates 854.2.4 Oxidation of Alkenes 894.3 Biocatalytic Oxidations with Hydrogen Peroxide 924.3.1 Why Enzymes and HOOH? 924.3.2 Biocatalytic Sulfoxidation 954.3.3 Biocatalytic Alkenes Epoxidation 964.3.4 Biocatalytic Alcohols Oxidation 984.4 Conclusions 99Acknowledgments 99References 100Part II Hydrogenation and Reduction Reactions 1035 Asymmetric Hydrogenation of Dehydroamino acid Derivatives by Rh-Catalystswith Chiral Monodentate P-Ligands 105Serafino Gladiali, Elisabetta Alberico, and Ilya Gridnev5.1 Introduction 1055.2 Chiral Monodentate Phosphorus Ligands in Asymmetric Hydrogenation 1085.3 Catalyst Precursors 1125.4 Mechanistic Insights 1175.5 Formation of the MAC Adducts 1215.6 Evolution of MAC-Adducts and Origin of Enantioselection 124References 1266 Recent Advances in the Synthesis and Catalytic Hydrogenation of Dehydroamino Acid Derivatives and Bicyclo[2.2.2]octenes 131V ronique Michelet, Virginie Ratovelomanana-Vidal, Vasile I. PÃórvulescu, and Marijan Kocevar6.1 Introduction 1316.2 Synthesis of DDAA Derivatives and Bicyclo[2.2.2]octenes 1336.3 Ligands 1336.4 Homogeneous Hydrogenation and Hydrogenolysis Reactions with Dehydroamino Acid Derivatives and Bicyclo[2.2.2]oct-7-enes over Nanocolloids-Modified Catalysts 1366.4.1 Nanometal Colloids-Modified Catalysts 1366.4.2 Nanooxide Colloids-Modified Catalysts 1406.5 Heterogeneous Catalysts for Hydrogenolysis of Bicyclo[2.2.2]oct-7-enes 1426.5.1 Heterogeneized Ligand-Modified Nanoclusters 1426.6 Layered-Double Hydroxides as a Support for Rh(TPPTS)3 and Rh-(m-TPPTC)3 Homogeneous Catalysts 1446.7 Conclusions 147Acknowledgments 147References 1487 Ir-Catalyzed Hydrogenation of Minimally Functionalized Olefins Using Phosphite-Nitrogen Ligands 153Montserrat Díeguez, Pher G. Andersson, and Oscar Pà mies7.1 Introduction 1537.2 Application of Phosphite-Nitrogen Ligands 1557.3 Conclusions 161Acknowledgments 163References 1638 Modeling in Homogeneous Catalysis: a Tutorial 167Eric Clot and Per-Ola Norrby8.1 Introduction 1678.2 Molecular Modeling 1678.3 Wave Function Theory, WFT 1688.4 Density Functional Theory, DFT 1698.5 Orbitals 1708.6 Basis Sets 1728.7 Solvation 1748.8 Analyzing the Reaction Energies 1758.9 Analyzing the Electronic Structure 1778.9.1 The NBO Method 1788.9.1.1 How Does It Work? 1788.9.1.2 Departure from the Lewis Structure 1808.9.1.3 NBO and Transition Metal Complexes 1838.9.2 The AIM Method 1878.9.2.1 How Does It Work? 1878.9.2.2 Nature of the Bonded Interaction 189References 190Part III C-C and C-Hetero Bond-Forming Reactions 1939 Golden Times for Allenes 195Norbert Krause9.1 Introduction 1959.2 Cyclization of Hydroxyallenes 1969.3 Cyclization of Aminoallenes 2039.4 Cyclization of Thioallenes 2069.5 Conclusion 206References 20710 Copper Catalysis in Arene and Heteroarene Functionalization through C-H Bond Activation 211Sandro Cacchi, Giancarlo Fabrizi, and Antonella Goggiamani10.1 Introduction 21110.2 C-C Bond-Forming Reactions 21210.2.1 Via (Hetero)aryl-H/R-X Coupling 21210.2.1.1 R-X=(Hetero)aryl Halides 21210.2.1.2 R-X=Alkenyl Bromides 21510.2.1.3 R-X=BrCH2Ar 21610.2.2 Via (Hetero)aryl-H/Ar2I+X- Coupling 21710.2.2.1 Direct (Hetero)arylation of Heteroarenes 21710.2.2.2 Direct Arylation of Arenes21810.2.3 Via (Hetero)aryl-H/C-H Coupling 21910.2.3.1 Dimerization of (Hetero)arenes 21910.2.3.2 Cyclization of Anilides 22010.2.3.3 Cyclization of N-aryl ß-Enaminones 22110.2.4 Via Aryl-H Addition to Terminal Alkynes 22310.3 C-N Bond-Forming Reactions 22310.4 C-O Bond-Forming Reactions 22710.5 C-Halogen Bond-Forming Reactions 229References 23011 Ligated Organocuprates: an A-Z Routemapof Mechanism and Application 233Simon Woodward and Darren Willcox11.1 Introduction 23311.2 Accepted Mechanistic Proposals 23311.2.1 Kinetic and NMR Studies23511.2.2 Computational Studies 24211.2.3 Nonlinear Effects 24311.2.4 Challenges 24511.3 Selective Applications in Privileged Copper(I) Catalysis 24511.3.1Conjugate Addition 24511.3.2 Additions to Allylic Halides 250References 25212Rh-, Ag-, and Cu-Catalyzed C-N Bond Formation 257Philippe Dauban, Camille Lescot, M. Mar Diaz-Requejo, and Pedro J. Perez12.1 Introduction 25712.2 Historical Background 25812.3 Copper- and Silver-Catalyzed C-N Bond Formation 26012.4 Rhodium-Catalyzed C-N Bond Formation 26512.5 Conclusions 273References 27413 Development of the Asymmetric Nozaki-Hiyama-Kishi Reaction 279GrÃíinne C. Hargaden and Patrick J. Guiry13.1 Introduction 27913.2 Development of a Catalytic Nozaki-Hiyama-Kishi Reaction 27913.3 Catalytic Enantioselective Nozaki-Hiyama-Kishi Reaction 28113.4 Application of Salen-Derived Ligands in the Enantioselective Nozaki-Hiyama-Kishi Reaction 28313.5 Application of Oxazoline-Containing Ligands in the Catalytic Enantioselective Nozaki-Hiyama-Kishi Reaction 28613.6Application of Tethered Bis(8-quinolinato) Chromium Complexes in the Catalytic Enantioselective Nozaki-Hiyama-Kishi 29913.7 Application of Chiral Spirocyclic Borate Ligands to the Catalytic Enantioselective Nozaki-Hiyama-Kishi Allylation 30313.8 Applications of Catalytic Nozaki-Hiyama-Kishi Reaction in Total Synthesis 30313.9 Conclusions 305References 30614 Chiral Imidate Ligands: Synthesis and Applications in Asymmetric Catalysis 309Timothy N el, Katrien Bert, Pieter Janssens, and Johan Van der Eycken14.1 Introduction 30914.2 Cyclic Imidates 31114.3 Synthesis of Imidates 31214.4 Synthesis of Imidate Ligands 31314.5Synthesis of Imidate-Copper (I) Complexes 31314.6 Application of Chiral Imidate Ligands in Enantioselective Catalysis 31514.6.1 Copper (I)-Catalyzed Asymmetric Aziridination 31514.6.2 Asymmetric Diethylzinc Addition 31614.6.3 Asymmetric Palladium(0)-Catalyzed Allylic Alkylations 31614.6.4 Asymmetric Iridium (I)-Catalyzed Hydrogenations 31814.7 Novel Synthetic Applications of Cyclic Imidates 32014.7.1 One-Step Synthesis of Chiral Oxazoline-Alcohol Ligands 32014.7.2 Synthesis of Chiral spiro-2-Alkoxy-Imidazolidines 32114.8 Conclusions 322References 32415 Catalyzed Organic Reactions in Ball Mills 327Achim Stolle, BerndOndruschka, Anke Krebs, and Carsten Bolm15.1 Introduction 32715.2 Acid- or Base-Catalyzed Reactions 32815.3 Organocatalytic Methods 33315.3.1 Asymmetric Aldol Reactions 33315.3.2 Cycloaddition and Related Reactions 33515.4 Metal-Catalyzed Reactions 33815.4.1 Suzuki-Miyaura Reaction 33815.4.2 Mizoroki-Heck Reaction 34015.4.3 Sonogashira Reaction 34115.4.4 Cu-Catalyzed Reactions 34315.4.5Miscellaneous Metal-Catalyzed Reactions 34515.5 Conclusion and Perspective 347References 348Index 351

• ISBN: 978-3-527-33097-3
• Editorial: Wiley-VCH
• Encuadernacion: Cartoné
• Páginas: 374
• Fecha Publicación: 04/04/2012
• Nº Volúmenes: 1
• Idioma: Inglés