Asymmetric Synthesis II: More Methods and Applications

After the overwhelming success of Asymmetric Synthesis - The Essentials, displaying a broad range of organic asymmetric syntheses, this is the second edition with latest subjects and authors. While the aim of the first edition was mainly to honor the achievements of the pioneers in asymmetric syntheses, the aim of this new edition was bringing the current developments, especially from younger colleagues, to the attention of students. The format of the book remained unchanged, i.e. short conceptual overviews by young leaders in their field including a short biography of the authors. The growing multidisciplinary research within chemistry is reflected in the selection of topics including metal catalysis, organocatalysis, physical organic chemistry, analytical chemistry, and its applications in total synthesis, materials research and industry. The prospective reader of this book is a graduate or undergraduate student of advanced organic chemistry as well as the industrial chemist who wants to get a brief update on the current developments in the field.

Table of Contents:
CATALYTIC ENANTIOSELECTIVE ALKYLATION OF PROCHIRAL KETONE ENOLATES Background Strategy and Results Asymmetric Allylic Alkylation in Total Synthesis Conclusions POINT-TO-PLANAR CHIRALITY TRANSFER IN TOTAL SYNTHESIS: SCALABLE AND PROGRAMMABLE SYNTHESIS OF HAOUAMINE A AND ITS ATROPISOMER Introduction Synthetic Strategy Featuring Point-to-Planar Chirality Transfer Programmable Synthesis of Haouamine A and Its Atropisomer TETHERED AMINOHYDROXYLATION Introduction and Background Tethered Aminohydroxylation Amide-Based Reoxidants Evidence for the Mechanism of the TA Reaction Applications in Organic Synthesis Conclusion and Future Work ORGANOCATALYZED TRANSFORMATIONS OF A, B-UNSATURATED CARBONYL COMPOUNDS THROUGH IMINIUM ION INTERMEDIATES THE RENAISSANCE OF SILICON-STEREOGENIC SILANES: A PERSONAL ACCOUNT Background Results Conclusion ASYMMETRIC DIENAMINE ACTIVATION Introduction Historic Background Results Conclusion ASYMMETRIC BR?NSTED ACID CATALYSIS Introduction and Background Strategy Results Summary QUATERNARY STEREOGENIC CENTERS BY ENANTIOSELECTIVE B-CARBON ELIMINATIONS FROM TERT-CYCLOBUTANOLS Background Objective: Enantioselective Formation of Quaternary Stereogenic Centers in Combination with Reactive Alkyl-Rhodium Intermediates Selective Generation of the Alkyl-Rhodium Species and Its Downstream Reactivities TOTAL SYNTHESIS OF OSELTAMIVIR AND ABT-341 USING ONE-POT TECHNOLOGY Introduction Results Conclusions ENANTIOSELECTIVE ANNULATIONS WITH CHIRAL N-MESITYL N-HETEROCYCLIC CARBENES Introduction Catalytic Generation of Chiral Enolate Equivalents Catalytic Generation of Homoenolate Equivalents Enantioselective Cascade Reactions Catalyzed by Chiral N-Heterocyclic Carbenes Catalytic Annulations via a, ?-Unsaturated Acyl Azoliums Conclusions ASYMMETRIC COUNTERANION-DIRECTED CATALYSIS (ACDC) Concept Application of ACDC to Organocatalysis Application of ACDC to Transition Metal Catalysis Application of ACDC to Lewis Acid Catalysis ENANTIOSELECTIVE ORGANO-SOMO CATALYSIS: A NOVEL ACTIVATION MODE FOR ASYMMETRIC SYNTHESIS Background Objective Results ENANTIOSELECTIVE PASSERINI REACTION Introduction Background Results Conclusion and Perspective RAPID ENANTIOMERIC EXCESS DETERMINATION ASYMMETRIC CATALYSIS OF REVERSIBLE REACTIONS Thermochemistry of Asymmetric Catalyses Close to the Equilibrium Kinetic Modeling of a Reversible Asymmetric Catalytic Reaction Case Study: a Reversible Asymmetric Organocatalytic Reaction Conclusions EXPLOITING FLUORINE CONFORMATIONAL EFFECTS IN ORGANOCATALYST DESIGN: THE FLUORINE?IMINIUM ION GAUCHE EFFECT DUTCH RESOLUTION CONSTRUCTION OF ANTI-ME-OH VICINAL RELATIONSHIPS IN POLYKETIDES Introduction Marshall - Tamaru Reaction Conclusions PHOTOSWITCHABLE GENERAL BASE CATALYSTS Introduction and Background Strategy and Results Outlook ASYMMETRIC HALONIUM ADDITION TO OLEFINS Introduction Intramolecular Lactonizations, Etherifications, and Aminations Polyene Cyclizations Intermolecular Additions to Alkenes Conclusion CATALYTIC ASYMMETRIC GOSTELI - CLAISEN REARRANGEMENT (CAGC) BIOMIMETIC TOTAL SYNTHESIS OF THE PENIFULVIN FAMILY Introduction The Penifulvin Family: Isolation and Biogenetic Origin Total Syntheses of Penifulvins A, B, and C Summary CATALYST-CONTROLLED 1,3-POLYOL SYNTHESES ENANTIOSELECTIVE CARBONYL ALLYLATION AND CROTYLATION FROM THE ALCOHOL OXIDATION LEVEL VIA C?C BOND FORMING TRANSFER HYDROGENATION Introduction and Background Strategy Results STEREOSELECTIVE SYNTHESIS WITH HYPERVALENT IODINE REAGENTS ASYMMETRIC GOLD-CATALYZED REACTIONS Introduction Diphosphine-Gold Complexes in Enantioselective Catalysis Monophosphine-Gold Complexes in Enantioselective Catalysis ASYMMETRIC CATALYSIS IN THE TOTAL SYNTHESIS OF LIPIDS AND POLYKETIDES Background Tuberculostearic Acid: One Isolated Methyl Group Ant Pheromones: Vicinal Methyl Branches Deoxypropionates: 1,3-Methyl Arrays Membrane-Spanning Lipids: 1,4-Dimethyl Units Saturated Isoprenoids: 1,5-Methyl Arrays THE EVOLVING ROLE OF BIOCATALYSIS IN ASYMMETRIC SYNTHESIS Background - First- and Second-Generation Biotransformations Results - Third-Generation Biotransformations Conclusions and Future Perspectives BIFUNCTIONAL THIOUREA CATALYSTS Background Results CATALYTIC ASYMMETRIC (4 + 3) CYCLOADDITIONS USING ALLENAMIDES Introduction and Background Strategy Results Conclusion APPLICATION OF THE ACHMATOWICZ REARRANGEMENT FOR THE SYNTHESIS OF OLIGOSACCHARIDES Introduction De novo Approach to Carbohydrates An Iterative Pd-Catalyzed Glycosylation and Bidirectional Postglycosylation Application to the Synthesis of the Anthrax Tetrasaccharide ASYMMETRIC C - C BOND FORMATION USING CHIRAL PHOSPHORIC ACID Background Results Conclusions and Future Perspectives ASYMMETRIC C - H BOND FUNCTIONALIZATION Background Results Conclusions and Future Perspectives ASYMMETRIC C - C BOND FORMATION USING CHIRAL GUANIDINE CATALYSTS Background Catalyst Design and Results ENANTIOSELECTIVE SYNTHESIS OF LACTONES VIA RH-CATALYZED KETONE HYDROACYLATION Background and Introduction Strategy and Results Conclusions and Future Directions RADICAL HALOALKYLATION ASYMMETRIC HYDROVINYLATION OF ALKENES Introduction New Protocols for the Heterodimerization of Ethylene/Propylene and Vinylarenes, 1,3-Dienes, and Norbornene Catalytic Asymmetric Hydrovinylation Reactions: Effects of Hemilabile Ligands All-Carbon Quaternary Centers via Catalytic Asymmetric HV Hydrovinylation (HV) of 1,3-Dienes and Asymmetric Variations Asymmetric Hydrovinylation of Unactivated Linear 1,3-Dienes Using Co(II) Catalysis Scope and Applications of Hydrovinylation Reactions: Exocyclic Stereocontrol A Stereoselective Route to either Steroid-C20(S) or -C20(R) Derivatives Asymmetric Hydrovinylation of Strained Alkenes Conclusions and Future Perspectives HETEROCYCLE CONSTRUCTION VIA ASYMMETRIC RHODIUM-CATALYZED CYCLOADDITIONS Background Strategy Results Application to Other Reactions Conclusion and Future Perspectives N-HETEROCYCLIC CARBENE-CATALYZED ALDOL DESYMMETRIZATIONS Introduction Strategy and Results Application to the Syntheses of Bakkenolides I, J, and S Conclusion STRATEGIES FOR THE ASYMMETRIC TOTAL SYNTHESIS OF NATURAL PRODUCTS: `'CHIRAL POOL' VERSUS CHIRAL CATALYSTS Introduction Catalytic Stereoselective Total Synthesis Natural Product Synthesis Starting from Chiral, Nonracemic Starting Materials Conclusion DYNAMIC KINETIC ASYMMETRIC TRANSFORMATIONS INVOLVING CARBON - CARBON BOND CLEAVAGE Background Donor - Acceptor Cyclopropanes as DYKAT Substrates Lewis Acid Catalysis Palladium Catalysis Deracemization of Tertiary Propargyl-Allyl Alcohols via Rhodium-Catalyzed Sequential Rearrangement/Enantioselective Conjugate Addition Conclusion IRON-CATALYZED ALLYLIC SUBSTITUTIONS Allylic Substitutions Catalyzed by the Hieber-Anion [Fe(CO)3(NO)]- Allylic Substitutions Catalyzed by Fe2(CO)9 ASYMMETRIC CONIA-ENE CARBOCYCLIZATIONS Introduction and Background: the Conia-ene Reaction Strategy: Organo/Metal Cooperative Catalysis Results TACTICS AND STRATEGIES IN THE TOTAL SYNTHESIS OF CHLOROSULFOLIPIDS Background Stereoselective Synthesis of vic-Dichloride Fragments Total Synthesis of Hexachlorosulfolipid Conclusions LINEAR FREE ENERGY RELATIONSHIPS (LFERS) IN ASYMMETRIC CATALYSIS Introduction and Background Hammett Electronic Parameters and Their Application to (salen)Mn(III)-Catalyzed Asymmetric Epoxidation Reactions Relating Br?nsted Acidity to Enantiomeric Ratio in an Asymmetric Hydrogen-Bond-Catalyzed Diels-Alder Reaction An LFER Describing the Influence of Steric Bulk in a Nozaki?Hiyama - Kishi Asymmetric Allylation of Acetophenone Correlating Quadrupole Moment to Enantioselectivity in Cation-p-Mediated Asymmetric Polycyclization Simultaneously Correlating Hammett and Charton Parameters to Enantioselectivity in Two-Dimensional Free Energy Relationships Conclusions ASYMMETRIC DIAMINATION OF ALKENES Introduction and Background Strategy Results ENZYMATIC ASYMMETRIC SYNTHESIS OF TERTIARY ALCOHOLS Introduction YerE - a Unique ThDP-Dependent Enzyme Hydroxynitrile Lyases Conclusion OXIDATIVE DEAROMATIZATION AND ORGANOCATALYTIC DESYMMETRIZATION Introduction Desymmetrization of Cyclohexadienones A One-Pot Oxidative Dearomatization and Catalytic Desymmetrization Oxo- and Aza-Michael Additions Further One-Pot Methods for Oxidative Dearomatization and Catalytic Desymmetrization Alkylative Dearomatization Summary TOTAL SYNTHESIS OF ALL (-)-AGELASTATIN ALKALOIDS Introduction Biosynthetically Inspired Plan for Total Synthesis Total Synthesis of the Agelastatin Alkaloids

About the Author :
Stefan Brase studied chemistry in Bangor, UK, Marseille, France, and Gottingen, Germany, where he gained his doctorate under Armin de Meijere in 1995. After post-doctoral appointments at Uppsala University, Sweden under J.-E. Backvall and The Scripps Research Institute, La Jolla, USA with K. C. Nicolaou, he began his research career at the RWTH Aachen with Dieter Enders in 1997, obtaining his lecturing qualification in 2001. He became a professor at the University of Bonn that same year and since 2003 he has been Full Professor at the Karlsruhe Institute of Technology. Professor Brase has more than 250 publications to his name and is a recipient of the ORCHEM award. His research interests include methods in drug discovery, combinatorial chemistry with a focus on the synthesis of biologically active compounds, total synthesis of natural products and nanotechnology. Mathias Christmann studied chemistry at the Technical University of Braunschweig and received a PhD from the Leibniz University of Hannover with Markus Kalesse. After postdoctoral research with Craig J. Forsyth at the University of Minnesota, USA, he joined the RWTH Aachen University as a Liebig Fellow of the Fonds der Chemischen Industrie, working towards his lecturing qualifi cation under Dieter Enders. In 2008, he was appointed Associate Professor at the Dortmund University of Technology, where he lectures in organic chemistry. Professor Christmann's research interests include organocatalysis, natural products synthesis and sustainable chemistry.