Asymmetric Synthesis. Vol.2

Stefan Bräse studied chemistry in Bangor, UK, Marseille, France, and Göttingen, Germany, where he gained his doctorate under Armin de Meijere in 1995. After post-doctoral appointments at Uppsala University, Sweden under J.-E. Bäckvall 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 lecturingqualification 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 Bräse 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 DieterEnders. 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.

Eine Gruppe international renommierter Autoren vermittelt die neuesten Forschungsergebnisse im Bereich der asymmetrischen Synthese. Studenten höherer Semester und Forscher finden in diesem Lehrbuch eine einzigartige Themensammlung, u. a. auch zu Anwendungen in der Industrie.

An illustrious group of international authors provides the reader with the latest research highlights in asymmetric synthesis. Both graduate students and advanced researchers will profit from a unique coverage of topics including industrial applications.

CATALYTIC ENANTIOSELECTIVE ALKYLATION OF PROCHIRAL KETONE ENOLATESBackgroundStrategy and ResultsAsymmetric Allylic Alkylation in Total SynthesisConclusionsPOINT-TO-PLANAR CHIRALITY TRANSFER IN TOTAL SYNTHESIS: SCALABLE AND PROGRAMMABLE SYNTHESIS OF HAOUAMINE A AND ITS ATROPISOMERIntroductionSynthetic Strategy Featuring Point-to-Planar Chirality TransferProgrammable Synthesis of Haouamine A and Its AtropisomerTETHERED AMINOHYDROXYLATIONIntroduction and BackgroundTethered AminohydroxylationAmide-Based ReoxidantsEvidence for the Mechanism of the TA ReactionApplications in Organic SynthesisConclusion and Future WorkORGANOCATALYZED TRANSFORMATIONS OF A, B-UNSATURATED CARBONYL COMPOUNDS THROUGH IMINIUM ION INTERMEDIATESTHE RENAISSANCE OF SILICON-STEREOGENIC SILANES: A PERSONAL ACCOUNTBackgroundResultsConclusionASYMMETRIC DIENAMINE ACTIVATIONIntroductionHistoric BackgroundResultsConclusionASYMMETRIC BRØNSTED ACID CATALYSISIntroduction and BackgroundStrategyResultsSummaryQUATERNARY STEREOGENIC CENTERS BY ENANTIOSELECTIVE B-CARBON ELIMINATIONS FROM TERT-CYCLOBUTANOLSBackgroundObjective: Enantioselective Formation of Quaternary Stereogenic Centers in Combination with Reactive Alkyl-RhodiumIntermediatesSelective Generation of the Alkyl-Rhodium Species and Its Downstream ReactivitiesTOTAL SYNTHESIS OF OSELTAMIVIR AND ABT-341 USING ONE-POT TECHNOLOGYIntroductionResultsConclusionsENANTIOSELECTIVE ANNULATIONS WITH CHIRAL N-MESITYL N-HETEROCYCLIC CARBENESIntroductionCatalytic Generation of Chiral Enolate EquivalentsCatalytic Generation of Homoenolate EquivalentsEnantioselective Cascade Reactions Catalyzed by Chiral N-Heterocyclic CarbenesCatalytic Annulations via a, ß-Unsaturated Acyl AzoliumsConclusionsASYMMETRIC COUNTERANION-DIRECTED CATALYSIS (ACDC)ConceptApplication of ACDC to OrganocatalysisApplication of ACDC to Transition Metal CatalysisApplication of ACDC to Lewis Acid CatalysisENANTIOSELECTIVE ORGANO-SOMO CATALYSIS: A NOVEL ACTIVATION MODE FOR ASYMMETRIC SYNTHESISBackgroundObjectiveResultsENANTIOSELECTIVE PASSERINI REACTIONIntroductionBackgroundResultsConclusion and PerspectiveRAPID ENANTIOMERIC EXCESS DETERMINATIONASYMMETRIC CATALYSIS OF REVERSIBLE REACTIONSThermochemistry of Asymmetric Catalyses Close to the EquilibriumKinetic Modeling of a Reversible Asymmetric Catalytic ReactionCase Study: a Reversible Asymmetric Organocatalytic ReactionConclusionsEXPLOITING FLUORINE CONFORMATIONAL EFFECTS IN ORGANOCATALYST DESIGN: THE FLUORINE?IMINIUM ION GAUCHE EFFECTDUTCH RESOLUTIONCONSTRUCTION OF ANTI-ME-OH VICINAL RELATIONSHIPS IN POLYKETIDESIntroductionMarshall - Tamaru ReactionConclusionsPHOTOSWITCHABLE GENERAL BASE CATALYSTSIntroduction and BackgroundStrategy and ResultsOutlookASYMMETRIC HALONIUM ADDITION TO OLEFINSIntroductionIntramolecular Lactonizations, Etherifications, and AminationsPolyene CyclizationsIntermolecular Additions to AlkenesConclusionCATALYTIC ASYMMETRIC GOSTELI - CLAISEN REARRANGEMENT (CAGC)BIOMIMETIC TOTAL SYNTHESIS OF THE PENIFULVIN FAMILYIntroductionThe Penifulvin Family: Isolation and Biogenetic OriginTotal Syntheses of Penifulvins A, B, and CSummaryCATALYST-CONTROLLED 1,3-POLYOL SYNTHESESENANTIOSELECTIVE CARBONYL ALLYLATION AND CROTYLATION FROM THE ALCOHOL OXIDATION LEVEL VIA C?C BOND FORMING TRANSFER HYDROGENATIONIntroduction and BackgroundStrategyResultsSTEREOSELECTIVE SYNTHESIS WITH HYPERVALENT IODINE REAGENTSASYMMETRIC GOLD-CATALYZED REACTIONSIntroductionDiphosphine-Gold Complexes in Enantioselective CatalysisMonophosphine-Gold Complexes in Enantioselective CatalysisASYMMETRIC CATALYSIS IN THE TOTAL SYNTHESIS OF LIPIDS AND POLYKETIDESBackgroundTuberculostearic Acid: One Isolated Methyl GroupAnt Pheromones: Vicinal Methyl BranchesDeoxypropionates: 1,3-Methyl ArraysMembrane-Spanning Lipids: 1,4-Dimethyl UnitsSaturated Isoprenoids: 1,5-Methyl ArraysTHE EVOLVING ROLE OF BIOCATALYSIS IN ASYMMETRIC SYNTHESISBackground - First- and Second-Generation BiotransformationsResults - Third-Generation BiotransformationsConclusions and Future PerspectivesBIFUNCTIONAL THIOUREA CATALYSTSBackgroundResultsCATALYTIC ASYMMETRIC (4 + 3) CYCLOADDITIONS USING ALLENAMIDESIntroduction and BackgroundStrategyResultsConclusionAPPLICATION OF THE ACHMATOWICZ REARRANGEMENT FOR THE SYNTHESIS OF OLIGOSACCHARIDESIntroductionDe novo Approach to CarbohydratesAn Iterative Pd-Catalyzed Glycosylation and Bidirectional PostglycosylationApplication to the Synthesis of the Anthrax TetrasaccharideASYMMETRIC C - C BOND FORMATION USING CHIRAL PHOSPHORIC ACIDBackgroundResultsConclusions and Future PerspectivesASYMMETRIC C - H BOND FUNCTIONALIZATIONBackgroundResultsConclusions and Future PerspectivesASYMMETRIC C - C BOND FORMATION USING CHIRAL GUANIDINE CATALYSTSBackgroundCatalyst Design and ResultsENANTIOSELECTIVE SYNTHESIS OF LACTONES VIA RH-CATALYZED KETONE HYDROACYLATIONBackground and IntroductionStrategy and ResultsConclusions and Future DirectionsRADICAL HALOALKYLATIONASYMMETRIC HYDROVINYLATION OF ALKENESIntroductionNew Protocols for the Heterodimerization of Ethylene/Propylene and Vinylarenes, 1,3-Dienes, and NorborneneCatalytic Asymmetric Hydrovinylation Reactions: Effects of Hemilabile LigandsAll-Carbon Quaternary Centers via Catalytic Asymmetric HVHydrovinylation (HV) of 1,3-Dienes and Asymmetric VariationsAsymmetric Hydrovinylation of Unactivated Linear 1,3-Dienes Using Co(II) CatalysisScope and Applications of Hydrovinylation Reactions: Exocyclic StereocontrolA Stereoselective Route to either Steroid-C20(S) or -C20(R) DerivativesAsymmetric Hydrovinylation of Strained AlkenesConclusions and Future PerspectivesHETEROCYCLE CONSTRUCTION VIA ASYMMETRIC RHODIUM-CATALYZED CYCLOADDITIONSBackgroundStrategyResultsApplication to Other ReactionsConclusion and Future PerspectivesN-HETEROCYCLIC CARBENE-CATALYZED ALDOL DESYMMETRIZATIONSIntroductionStrategy and ResultsApplication to the Syntheses of Bakkenolides I, J, and SConclusionSTRATEGIES FOR THE ASYMMETRIC TOTAL SYNTHESIS OF NATURAL PRODUCTS: `'CHIRAL POOL' VERSUS CHIRAL CATALYSTSIntroductionCatalytic Stereoselective Total SynthesisNatural Product Synthesis Starting from Chiral, Nonracemic Starting MaterialsConclusionDYNAMIC KINETIC ASYMMETRIC TRANSFORMATIONS INVOLVING CARBON - CARBON BOND CLEAVAGEBackgroundDonor - Acceptor Cyclopropanes as DYKAT SubstratesLewis Acid CatalysisPalladium CatalysisDeracemization of Tertiary Propargyl-Allyl Alcohols via Rhodium-Catalyzed Sequential Rearrangement/Enantioselective Conjugate AdditionConclusionIRON-CATALYZED ALLYLIC SUBSTITUTIONSAllylic Substitutions Catalyzed by the Hieber-Anion [Fe(CO)3(NO)]-Allylic Substitutions Catalyzed by Fe2(CO)9ASYMMETRIC CONIA-ENE CARBOCYCLIZATIONSIntroduction and Background: the Conia-ene ReactionStrategy: Organo/Metal Cooperative CatalysisResultsTACTICS AND STRATEGIES IN THE TOTAL SYNTHESIS OF CHLOROSULFOLIPIDSBackgroundStereoselective Synthesis of vic-Dichloride FragmentsTotal Synthesis of HexachlorosulfolipidConclusionsLINEAR FREE ENERGY RELATIONSHIPS (LFERS) IN ASYMMETRIC CATALYSISIntroduction and BackgroundHammett Electronic Parameters and Their Application to (salen)Mn(III)-Catalyzed Asymmetric Epoxidation ReactionsRelating Brønsted Acidity to Enantiomeric Ratio in an Asymmetric Hydrogen-Bond-Catalyzed Diels-Alder ReactionAn LFER Describing the Influence of Steric Bulk in a Nozaki?Hiyama - Kishi Asymmetric Allylation of AcetophenoneCorrelating Quadrupole Moment to Enantioselectivity in Cation-p-Mediated Asymmetric PolycyclizationSimultaneously Correlating Hammett and Charton Parameters to Enantioselectivity in Two-Dimensional Free Energy RelationshipsConclusionsASYMMETRIC DIAMINATION OF ALKENESIntroduction and BackgroundStrategyResultsENZYMATIC ASYMMETRIC SYNTHESIS OF TERTIARY ALCOHOLSIntroductionYerE - a Unique ThDP-Dependent EnzymeHydroxynitrile LyasesConclusionOXIDATIVE DEAROMATIZATION AND ORGANOCATALYTIC DESYMMETRIZATIONIntroductionDesymmetrization of CyclohexadienonesA One-Pot Oxidative Dearomatization and Catalytic DesymmetrizationOxo- and Aza-Michael AdditionsFurther One-Pot Methods for Oxidative Dearomatization and Catalytic DesymmetrizationAlkylative DearomatizationSummaryTOTAL SYNTHESIS OF ALL (-)-AGELASTATIN ALKALOIDSIntroductionBiosynthetically Inspired Plan for Total SynthesisTotal Synthesis of the Agelastatin Alkaloids