Innovative Catalysis in Organic Synthesis
Oxidation, Hydrogenation, and C-X Bond Forming Reactions

C-H, C-O, C-C, and C-Heteroatom bond forming processes by using metal-ligand approaches for the synthesis of organic compounds of
biological, pharmacological and organic nanotechnological utility are the key areas addressed in this book. Authored by a European team
of leaders in the field, it brings together innovative approaches for a variety of catalysis reactions and processes frequently applied in organic
synthesis into a handy reference work. It covers all major types of catalysis, including homogeneous, heterogeneous, and organocatalysis, as
well as mechanistic and computational studies. Special attention is paid to the improvements in efficiency and sustainability of important
catalytic processes, such as selective oxidations, hydrogenation, and cross-coupling reactions, and to their utilization in industry.

The result is a valuable resource for advanced researchers in both academia and industry, as well as graduate students in organic chemistry
aiming for chemo-, regio- or stereoselective synthesis of organic compounds by using novel catalytic systems.

FOREWORD

PART I: Oxidation Reactions

POLYOXOMETALATES AS HOMOGENEOUS OXIDATION CATALYSTS
Soluble Metal Oxides as Oxidation Catalysts
Homogeneous Oxidations with POMs Based Only on Mo(VI), W(VI), V(V) Addenda Ions
Homogeneous Oxidations with TMS-POMs
Conclusions

BIOINSPIRED OXIDATIONS CATALYZED BY NONHEME IRON AND MANGANESE COMPLEXES
Introduction
Catalytic Oxidation of C = C Bonds by Nonheme Iron and Manganese Complexes
Catalytic Oxidation of C -
H Bonds by Nonheme Iron and Manganese Complexes

THE FABULOUS DESTINY OF SULFENIC ACIDS
Introduction
Synthesis of Stable Sulfenic Acids
Generation of Transient Sulfenic Acids
Reactivity of Sulfenic Acids in the Preparation of Sulfoxides and Unsymmetrical Disulfides
Synthesis of Stable Sulfenate Anions
Generation of Transient Sulfenate Anions Leading to Sulfoxides
Conclusions

SUSTAINABLE CATALYTIC OXIDATIONS WITH PEROXIDES
Introduction
Metal-Based Selective Oxidations
Biocatalytic Oxidations with Hydrogen Peroxide
Conclusions

PART II: Hydrogenation and Reduction Reactions

ASYMMETRIC HYDROGENATION OF DEHYDROAMINO ACID DERIVATIVES BY RH-CATALYSTS WITH CHIRAL MONODENTATE P-LIGANDS
Introduction
Chiral Monodentate Phosphorus Ligands in Asymmetric Hydrogenation
Catalyst Precursors
Mechanistic Insights
Formation of the MAC Adducts
Evolution of MAC-Adducts and Origin of Enantioselection

RECENT ADVANCES IN THE SYNTHESIS AND CATALYTIC HYDROGENATION OF DEHYDROAMINO ACID DERIVATIVES AND BICYCLO[2.2.2]OCTENES
Introduction
Synthesis of DDAA Derivatives and Bicyclo[2.2.2]octenes
Ligands
Homogeneous Hydrogenation and Hydrogenolysis Reactions with Dehydroamino Acid Derivatives and Bicyclo[2.2.2]oct-7-enes over Nanocolloids-Modified Catalysts
Heterogeneous Catalysts for Hydrogenolysis of Bicyclo[2.2.2]oct-7-enes
Layered-Double Hydroxides as a Support for Rh(TPPTS)3 and Rh-(m-TPPTC)3 Homogeneous Catalysts
Conclusions

IR-CATALYZED HYDROGENATION OF MINIMALLY FUNCTIONALIZED OLEFINS USING PHOSPHITE -
NITROGEN LIGANDS
Introduction
Application of Phosphite -
Nitrogen Ligands
Conclusions

MODELING IN HOMOGENEOUS CATALYSIS: A TUTORIAL
Introduction
Molecular Modeling
Wave Function Theory, WFT
Density Functional Theory, DFT
Orbitals
Basis Sets
Solvation
Analyzing the Reaction Energies
Analyzing the Electronic Structure

PART III: C -
C and C -
Hetero bond-Forming Reactions

GOLDEN TIMES FOR ALLENES
Introduction
Cyclization of Hydroxyallenes
Cyclization of Aminoallenes
Cyclization of Thioallenes
Conclusion

COPPER CATALYSIS IN ARENE AND HETEROARENE FUNCTIONALIZATION THROUGH
C -
H BOND ACTIVATION
Introduction
C -
C Bond-Forming Reactions
C -
N Bond-Forming Reactions
C -
O Bond-Forming Reactions
C -
Halogen Bond-Forming Reactions

LIGATED ORGANOCUPRATES: AN A -
Z ROUTEMAP OF MECHANISM AND APPLICATION
Introduction
Accepted Mechanistic Proposals
Selective Applications in Privileged Copper(I) Catalysis

RH-, AG-, AND CU-CATALYZED C -
N BOND FORMATION
Introduction
Historical Background
Copper- and Silver-Catalyzed C -
N Bond Formation
Rhodium-Catalyzed C -
N Bond Formation
Conclusions

DEVELOPMENT OF THE ASYMMETRIC NOZAKI -
HIYAMA -
KISHI REACTION
Introduction
Development of a Catalytic Nozaki -
Hiyama -
Kishi Reaction
Catalytic Enantioselective Nozaki -
Hiyama -
Kishi Reaction
Application of Salen-Derived Ligands in the Enantioselective Nozaki -
Hiyama -
Kishi Reaction
Application of Oxazoline-Containing Ligands in the Catalytic Enantioselective Nozaki -
Hiyama -
Kishi Reaction
Application of Tethered Bis(8-quinolinato) Chromium Complexes in the Catalytic Enantioselective Nozaki -
Hiyama -
Kishi
Application of Chiral Spirocyclic Borate Ligands to the Catalytic Enantioselective Nozaki -
Hiyama -
Kishi Allylation
Applications of Catalytic Nozaki -
Hiyama -
Kishi Reaction in Total Synthesis
Conclusions

CHIRAL IMIDATE LIGANDS: SYNTHESIS AND APPLICATIONS IN ASYMMETRIC CATALYSIS
Introduction
Cyclic Imidates
Synthesis of Imidates
Synthesis of Imidate Ligands
Synthesis of Imidate -
Copper (I) Complexes
Application of Chiral Imidate Ligands in Enantioselective Catalysis
Novel Synthetic Applications of Cyclic Imidates
Conclusions

CATALYZED ORGANIC REACTIONS IN BALL MILLS
Introduction
Acid- or Base-Catalyzed Reactions
Organocatalytic Methods
Metal-Catalyzed Reactions
Conclusion and Perspective

Pher G. Andersson holds a chair at the Department of Biochemistry and Organic Chemistry at Uppsala University, Sweden. He received his Ph.D. in 1991 and became a lecturer at Uppsala University in 1994 and a Professor in 1997. Among his many awards are the Bjurzons award (1992), the Oscar award (1995), the Junior Individual Grant for outstanding young researchers (1997), and the Astra Zeneca Research
Award in Organic Chemistry (2004). He was Chairman of the management committee for the COST D24 program 'Sustainable Chemical Processes: Stereoselective Transition Metal-Catalyzed Reactions' which ran from 2001-2006 and he was the Coordinator for the 'Excellent Nordic Chemistry Network'. Since 2011 he also holds a position as Honorary Research Professor at UKZN, South Africa. Pher Andersson
has authored more than 100 publications and edited the books 'Modern Reduction Methods' (Wiley-VCH, 2008) together with his former co-worker Ian Munslow and 'ridium Catalysis' (Springer, 2010). His research interests cover selective synthesis, asymmetric catalysis, and sustainable chemistry.