Innovative Catalysis in Organic Synthesis -- Contents -- Foreword -- List of Contributors -- Part I Oxidation Reactions -- 1 Polyoxometalates as Homogeneous Oxidation Catalysts -- 1.1 Soluble Metal Oxides as Oxidation Catalysts -- 1.2 Homogeneous Oxidations with POMs Based Only on Mo(VI), W(VI), V(V) Addenda Ions -- 1.2.1 Oxidation with Hydrogen Peroxide by Peroxopolyoxotungstates-Dendrimers -- 1.2.2 Homogeneous Oxidation with Hydrogen Peroxide in the Presence of Vacant and Hybrid POMs -- 1.3 Homogeneous Oxidations with TMS-POMs -- 1.3.1 Peroxopolyoxometalates of Hf/Zr -- 1.3.2 Aerobic Oxidations with Polyoxopalladates -- 1.3.3 TMSPs as Oxygen-Evolving Catalysts -- 1.4 Conclusions -- Acknowledgments -- References -- 2 Bioinspired Oxidations Catalyzed by Nonheme Iron and Manganese Complexes -- 2.1 Introduction -- 2.2 Catalytic Oxidation of C=C Bonds by Nonheme Iron and Manganese Complexes -- 2.2.1 Epoxidation -- 2.2.1.1 Iron-Based Catalysts -- 2.2.1.2 Manganese-Based Catalysts -- 2.2.2 cis-Dihydroxylation -- 2.2.2.1 Iron-Based Catalysts -- 2.2.2.2 Manganese-Based Catalysts -- 2.3 Catalytic Oxidation of C-H Bonds by Nonheme Iron and Manganese Complexes -- 2.3.1 Hydroxylation -- 2.3.1.1 Iron-Based Catalysts -- 2.3.1.2 Manganese-Based Catalysts -- 2.3.2 Desaturation -- 2.3.2.1 Iron-Based Catalysts -- 2.3.2.2 Manganese-Based Catalysts -- References -- 3 The Fabulous Destiny of Sulfenic Acids -- 3.1 Introduction -- 3.2 Synthesis of Stable Sulfenic Acids -- 3.3 Generation of Transient Sulfenic Acids -- 3.4 Reactivity of Sulfenic Acids in the Preparation of Sulfoxides and Unsymmetrical Disulfides -- 3.5 Synthesis of Stable Sulfenate Anions -- 3.6 Generation of Transient Sulfenate Anions Leading to Sulfoxides -- 3.7 Conclusions -- References -- 4 Sustainable Catalytic Oxidations with Peroxides -- 4.1 Introduction -- 4.2 Metal-Based Selective Oxidations.

4.2.1 Bromination Reactions -- 4.2.2 Oxidation of Nitrogen-Containing Substrates -- 4.2.3 Oxidation of Sulfur-Containing Substrates -- 4.2.4 Oxidation of Alkenes -- 4.3 Biocatalytic Oxidations with Hydrogen Peroxide -- 4.3.1 Why Enzymes and HOOH? -- 4.3.2 Biocatalytic Sulfoxidation -- 4.3.3 Biocatalytic Alkenes Epoxidation -- 4.3.4 Biocatalytic Alcohols Oxidation -- 4.4 Conclusions -- Acknowledgments -- References -- Part II Hydrogenation and Reduction Reactions -- 5 Asymmetric Hydrogenation of Dehydroamino acid Derivatives by Rh-Catalysts with Chiral Monodentate P-Ligands -- 5.1 Introduction -- 5.2 Chiral Monodentate Phosphorus Ligands in Asymmetric Hydrogenation -- 5.3 Catalyst Precursors -- 5.4 Mechanistic Insights -- 5.5 Formation of the MAC Adducts -- 5.6 Evolution of MAC-Adducts and Origin of Enantioselection -- References -- 6 Recent Advances in the Synthesis and Catalytic Hydrogenation of Dehydroamino Acid Derivatives and Bicyclo[2.2.2]octenes -- 6.1 Introduction -- 6.2 Synthesis of DDAA Derivatives and Bicyclo[2.2.2]octenes -- 6.3 Ligands -- 6.4 Homogeneous Hydrogenation and Hydrogenolysis Reactions with Dehydroamino Acid Derivatives and Bicyclo[2.2.2]oct-7-enes over Nanocolloids-Modified Catalysts -- 6.4.1 Nanometal Colloids-Modified Catalysts -- 6.4.2 Nanooxide Colloids-Modified Catalysts -- 6.5 Heterogeneous Catalysts for Hydrogenolysis of Bicyclo[2.2.2]oct-7-enes -- 6.5.1 Heterogeneized Ligand-Modified Nanoclusters -- 6.6 Layered-Double Hydroxides as a Support for Rh(TPPTS)3 and Rh-(m-TPPTC)3 Homogeneous Catalysts -- 6.7 Conclusions -- Acknowledgments -- References -- 7 Ir-Catalyzed Hydrogenation of Minimally Functionalized Olefins Using Phosphite-Nitrogen Ligands -- 7.1 Introduction -- 7.2 Application of Phosphite-Nitrogen Ligands -- 7.3 Conclusions -- Acknowledgments -- References -- 8 Modeling in Homogeneous Catalysis: a Tutorial.

8.1 Introduction -- 8.2 Molecular Modeling -- 8.3 Wave Function Theory, WFT -- 8.4 Density Functional Theory, DFT -- 8.5 Orbitals -- 8.6 Basis Sets -- 8.7 Solvation -- 8.8 Analyzing the Reaction Energies -- 8.9 Analyzing the Electronic Structure -- 8.9.1 The NBO Method -- 8.9.1.1 How Does It Work? -- 8.9.1.2 Departure from the Lewis Structure -- 8.9.1.3 NBO and Transition Metal Complexes -- 8.9.2 The AIM Method -- 8.9.2.1 How Does It Work? -- 8.9.2.2 Nature of the Bonded Interaction -- References -- Part III C-C and C-Hetero Bond-Forming Reactions -- 9 Golden Times for Allenes -- 9.1 Introduction -- 9.2 Cyclization of Hydroxyallenes -- 9.3 Cyclization of Aminoallenes -- 9.4 Cyclization of Thioallenes -- 9.5 Conclusion -- References -- 10 Copper Catalysis in Arene and Heteroarene Functionalization through C-H Bond Activation -- 10.1 Introduction -- 10.2 C-C Bond-Forming Reactions -- 10.2.1 Via (Hetero)aryl-H/R-X Coupling -- 10.2.1.1 R-X=(Hetero)aryl Halides -- 10.2.1.2 R-X=Alkenyl Bromides -- 10.2.1.3 R-X=BrCH2Ar -- 10.2.2 Via (Hetero)aryl-H/Ar2I+X- Coupling -- 10.2.2.1 Direct (Hetero)arylation of Heteroarenes -- 10.2.2.2 Direct Arylation of Arenes -- 10.2.3 Via (Hetero)aryl-H/C-H Coupling -- 10.2.3.1 Dimerization of (Hetero)arenes -- 10.2.3.2 Cyclization of Anilides -- 10.2.3.3 Cyclization of N-aryl β-Enaminones -- 10.2.4 Via Aryl-H Addition to Terminal Alkynes -- 10.3 C-N Bond-Forming Reactions -- 10.4 C-O Bond-Forming Reactions -- 10.5 C-Halogen Bond-Forming Reactions -- References -- 11 Ligated Organocuprates: An A-Z Routemap of Mechanism and Application -- 11.1 Introduction -- 11.2 Accepted Mechanistic Proposals -- 11.2.1 Kinetic and NMR Studies -- 11.2.2 Computational Studies -- 11.2.3 Nonlinear Effects -- 11.2.4 Challenges -- 11.3 Selective Applications in Privileged Copper(I) Catalysis -- 11.3.1 Conjugate Addition.

11.3.2 Additions to Allylic Halides -- References -- 12 Rh-, Ag-, and Cu-Catalyzed C-N Bond Formation -- 12.1 Introduction -- 12.2 Historical Background -- 12.3 Copper- and Silver-Catalyzed C-N Bond Formation -- 12.4 Rhodium-Catalyzed C-N Bond Formation -- 12.5 Conclusions -- References -- 13 Development of the Asymmetric Nozaki-Hiyama-Kishi Reaction -- 13.1 Introduction -- 13.2 Development of a Catalytic Nozaki-Hiyama-Kishi Reaction -- 13.3 Catalytic Enantioselective Nozaki-Hiyama-Kishi Reaction -- 13.4 Application of Salen-Derived Ligands in the Enantioselective Nozaki-Hiyama-Kishi Reaction -- 13.5 Application of Oxazoline-Containing Ligands in the Catalytic Enantioselective Nozaki-Hiyama-Kishi Reaction -- 13.6 Application of Tethered Bis(8-quinolinato) Chromium Complexes in the Catalytic Enantioselective Nozaki-Hiyama-Kishi -- 13.7 Application of Chiral Spirocyclic Borate Ligands to the Catalytic Enantioselective Nozaki-Hiyama-Kishi Allylation -- 13.8 Applications of Catalytic Nozaki-Hiyama-Kishi Reaction in Total Synthesis -- 13.9 Conclusions -- References -- 14 Chiral Imidate Ligands: Synthesis and Applications in Asymmetric Catalysis -- 14.1 Introduction -- 14.2 Cyclic Imidates -- 14.3 Synthesis of Imidates -- 14.4 Synthesis of Imidate Ligands -- 14.5 Synthesis of Imidate-Copper (I) Complexes -- 14.6 Application of Chiral Imidate Ligands in Enantioselective Catalysis -- 14.6.1 Copper (I)-Catalyzed Asymmetric Aziridination -- 14.6.2 Asymmetric Diethylzinc Addition -- 14.6.3 Asymmetric Palladium(0)-Catalyzed Allylic Alkylations -- 14.6.4 Asymmetric Iridium (I)-Catalyzed Hydrogenations -- 14.7 Novel Synthetic Applications of Cyclic Imidates -- 14.7.1 One-Step Synthesis of Chiral Oxazoline-Alcohol Ligands -- 14.7.2 Synthesis of Chiral spiro-2-Alkoxy-Imidazolidines -- 14.8 Conclusions -- References -- 15 Catalyzed Organic Reactions in Ball Mills.

15.1 Introduction -- 15.2 Acid- or Base-Catalyzed Reactions -- 15.3 Organocatalytic Methods -- 15.3.1 Asymmetric Aldol Reactions -- 15.3.2 Cycloaddition and Related Reactions -- 15.4 Metal-Catalyzed Reactions -- 15.4.1 Suzuki-Miyaura Reaction -- 15.4.2 Mizoroki-Heck Reaction -- 15.4.3 Sonogashira Reaction -- 15.4.4 Cu-Catalyzed Reactions -- 15.4.5 Miscellaneous Metal-Catalyzed Reactions -- 15.5 Conclusion and Perspective -- References -- Index.