Note: Intro -- Asymmetric Synthesis with Chemical and Biological Methods -- Foreword -- Contents -- Preface -- List of Contributors -- 1 Stoichiometric Asymmetric Synthesis -- 1.1 Development of Novel Enantioselective Synthetic Methods -- 1.1.1 Introduction -- 1.1.2 α-Silyl Ketone-Controlled Asymmetric Syntheses -- 1.1.2.1 Regio- and Enantioselective α-Fluorination of Ketones -- 1.1.2.2 α-Silyl Controlled Asymmetric Mannich Reactions -- 1.1.3 Asymmetric Hetero-Michael Additions -- 1.1.3.1 Asymmetric Aza-Michael Additions -- 1.1.3.2 Asymmetric Oxa-Michael Additions -- 1.1.3.3 Asymmetric Phospha-Michael Additions -- 1.1.4 Asymmetric Syntheses with Lithiated α-Aminonitriles -- 1.1.4.1 Asymmetric Nucleophilic α-Aminoacylation -- 1.1.4.2 Asymmetric Nucleophilic Alkenoylation of Aldehydes -- 1.1.5 Asymmetric Electrophilic α-Substitution of Lactones and Lactams -- 1.1.6 Asymmetric Synthesis of α-Phosphino Ketones and 2-Phosphino Alcohols -- 1.1.7 Asymmetric Synthesis of 1,3-Diols and anti-1,3-Polyols -- 1.1.8 Asymmetric Synthesis of α-Substituted Sulfonamides and Sulfonates -- 1.2 Asymmetric Synthesis of Natural Products Employing the SAMP/RAMP Hydrazone Methodology -- 1.2.1 Introduction -- 1.2.2 Stigmatellin A -- 1.2.3 Callistatin A -- 1.2.4 Dehydroiridodiol(dial) and Neonepetalactone -- 1.2.5 First Enantioselective Synthesis of Dendrobatid Alkaloids Indolizidine 209I and 223J -- 1.2.6 Efficient Synthesis of (2S,12´R)-2-(12´-Aminotridecyl)pyrrolidine, a Defense Alkaloid of the Mexican Bean Beetle -- 1.2.7 2-epi-Deoxoprosopinine -- 1.2.8 Attenol A and B -- 1.2.9 Asymmetric Synthesis of (+)- and (-)-Streptenol A -- 1.2.10 Sordidin -- 1.2.11 Prelactone B and V -- 1.3 Asymmetric Synthesis Based on Sulfonimidoyl-Substituted Allyltitanium Complexes -- 1.3.1 Introduction -- 1.3.2 Hydroxyalkylation of Sulfonimidoyl-Substituted Allylltitanium Complexes. , 1.3.2.1 Sulfonimidoyl-Substituted Bis(allyl)titanium Complexes -- 1.3.2.2 Sulfonimidoyl-Substituted Mono(allyl)tris(diethylamino)titanium Complexes -- 1.3.3 Aminoalkylation of Sulfonimidoyl-Substituted Allyltitanium Complexes -- 1.3.3.1 Sulfonimidoyl-Substituted Bis(allyl)titanium Complexes -- 1.3.3.2 Sulfonimidoyl-Substituted Mono(allyl)tris(diethylamino)titanium Complexes -- 1.3.4 Structure and Reactivity of Sulfonimidoyl-Substituted Allyltitanium Complexes -- 1.3.4.1 Sulfonimidoyl-Substituted Bis(allyl)titanium Complexes -- 1.3.4.2 Sulfonimidoyl-Substituted Mono(allyl)titanium Complexes -- 1.3.5 Asymmetric Synthesis of Homopropargyl Alcohols -- 1.3.6 Asymmetric Synthesis of 2,3-Dihydrofurans -- 1.3.7 Synthesis of Bicyclic Unsaturated Tetrahydrofurans -- 1.3.8 Asymmetric Synthesis of Alkenyloxiranes -- 1.3.9 Asymmetric Synthesis of Unsaturated Mono- and Bicyclic Prolines -- 1.3.10 Asymmetric Synthesis of Bicyclic Amino Acids -- 1.3.11 Asymmetric Synthesis of β-Amino Acids -- 1.3.12 Conclusion -- 1.4 The "Daniphos" Ligands: Synthesis and Catalytic Applications -- 1.4.1 Introduction -- 1.4.2 General Synthesis -- 1.4.3 Applications in Stereoselective Catalysis -- 1.4.3.1 Enantioselective Hydrogenations -- 1.4.3.2 Diastereoselective Hydrogenation of Folic Acid Ester -- 1.4.3.3 Enantioselective Isomerization of Geranylamine to Citronellal -- 1.4.3.4 Nucleophilic Asymmetric Ring-Opening of Oxabenzonorbornadiene -- 1.4.3.5 Enantioselective Suzuki Coupling -- 1.4.3.6 Asymmetric Hydrovinylation -- 1.4.3.7 Allylic Sulfonation -- 1.4.4 Conclusion -- 1.5 New Chiral Ligands Based on Substituted Heterometallocenes -- 1.5.1 Introduction -- 1.5.2 General Properties of Phosphaferrocenes -- 1.5.3 Synthesis of Phosphaferrocenes -- 1.5.4 Preparation of Bidentate P,P and P,N Ligands -- 1.5.5 Modification of the Backbone Structure. , 1.5.6 Cp-Phosphaferrocene Hybrid Systems -- 1.5.7 Catalytic Applications -- 1.5.8 Conclusion -- 2 Catalytic Asymmetric Synthesis -- 2.1 Chemical Methods -- 2.1.1 Sulfoximines as Ligands in Asymmetric Metal Catalysis -- 2.1.1.1 Introduction -- 2.1.1.2 Development of Methods for Sulfoximine Modification -- 2.1.1.3 Sulfoximines as Ligands in Asymmetric Metal Catalysis -- 2.1.1.4 Conclusions -- 2.1.2 Catalyzed Asymmetric Aryl Transfer Reactions -- 2.1.2.1 Introduction -- 2.1.2.2 Catalyst Design -- 2.1.2.3 Catalyzed Aryl Transfer Reactions -- 2.1.3 Substituted [2.2]Paracyclophane Derivatives as Efficient Ligands for Asymmetric 1,2- and 1,4-Addition Reactions -- 2.1.3.1 [2.2]Paracyclophanes as Chiral Ligands -- 2.1.3.2 Synthesis of [2.2]Paracyclophane Ligands -- 2.1.3.2.1 Preparation of FHPC-, AHPC-, and BHPC-Based Imines -- 2.1.3.2 Structural Information on AHPC-Based Imines -- 2.1.3.3 Asymmetric 1,2-Addition Reactions to Aryl Aldehydes -- 2.1.3.3.1 Initial Considerations -- 2.1.3.3.2 Asymmetric Addition Reactions to Aromatic Aldehydes: Scope of Substrates -- 2.1.3.4 Asymmetric Addition Reactions to Aliphatic Aldehydes -- 2.1.3.5 Addition of Alkenylzinc Reagents to Aldehydes -- 2.1.3.6 Asymmetric Conjugate Addition Reactions -- 2.1.3.7 Asymmetric Addition Reactions to Imines -- 2.1.3.8 Asymmetric Addition Reactions on Solid Supports -- 2.1.3.8.1 Applications -- 2.1.3.9 Conclusions and Future Perspective -- 2.1.4 Palladium-Catalyzed Allylic Alkylation of Sulfur and Oxygen Nucleophiles - Asymmetric Synthesis, Kinetic Resolution and Dynamic Kinetic Resolution -- 2.1.4.1 Introduction -- 2.1.4.2 Asymmetric Synthesis of Allylic Sulfones and Allylic Sulfides and Kinetic Resolution of Allylic Esters -- 2.1.4.2.1 Kinetic Resolution -- 2.1.4.2.2 Selectivity -- 2.1.4.2.3 Asymmetric Synthesis -- 2.1.4.2.4 Synthesis of Enantiopure Allylic Alcohols. , 2.1.4.3 Asymmetric Rearrangment and Kinetic Resolution of Allylic Sulfinates -- 2.1.4.3.1 Introduction -- 2.1.4.3.2 Synthesis of Racemic Allylic Sulfinates -- 2.1.4.3.3 Pd-Catalyzed Rearrangement -- 2.1.4.3.4 Kinetic Resolution -- 2.1.4.3.5 Mechanistic Considerations -- 2.1.4.4 Asymmetric Rearrangment of Allylic Thiocarbamates -- 2.1.4.4.1 Introduction -- 2.1.4.4.2 Synthesis of Racemic O-Allylic Thiocarbamates -- 2.1.4.4.3 Acyclic Carbamates -- 2.1.4.4.4 Cyclic Carbamates -- 2.1.4.4.5 Mechanistic Considerations -- 2.1.4.4.6 Synthesis of Allylic Sulfides -- 2.1.4.5 Asymmetric Synthesis of Allylic Thioesters and Kinetic Resolution of Allylic Esters -- 2.1.4.5.1 Introduction -- 2.1.4.5.2 Asymmetric Synthesis of Allylic Thioesters -- 2.1.4.5.3 Kinetic Resolution of Allylic Esters -- 2.1.4.5.4 Memory Effect and Dynamic Kinetic Resolution of the Five-Membered Cyclic Acetate -- 2.1.4.5.5 Asymmetric Synthesis of Cyclopentenyl Thioacetate -- 2.1.4.6 Kinetic and Dynamic Kinetic Resolution of Allylic Alcohols -- 2.1.4.6.1 Introduction -- 2.1.4.6.2 Asymmetric Synthesis of Symmetrical Allylic Alcohols -- 2.1.4.6.3 Asymmetric Synthesis of Unsymmetrical Allylic Alcohols -- 2.1.4.6.4 Asymmetric Synthesis of a Prostaglandin Building Block -- 2.1.4.6.5 Investigation of an Unsaturated Analogue of BPA -- 2.1.4.7 Conclusions -- 2.1.5 The QUINAPHOS Ligand Family and its Application in Asymmetric Catalysis -- 2.1.5.1 Introduction -- 2.1.5.2 Synthetic Strategy -- 2.1.5.3 Stereochemistry and Coordination Properties -- 2.1.5.3.1 Free Ligands -- 2.1.5.3.2 Complexes -- 2.1.5.4 Catalytic Applications -- 2.1.5.4.1 Rhodium-Catalyzed Asymmetric Hydroformylation of Styrene -- 2.1.5.4.2 Rhodium-Catalyzed Asymmetric Hydrogenation of Functionalized Alkenes -- 2.1.5.4.3 Ruthenium-Catalyzed Asymmetric Hydrogenation of Aromatic Ketones. , 2.1.5.4.4 Copper-Catalyzed Enantioselective Conjugate Addition of Diethylzinc to Enones -- 2.1.5.4.5 Nickel-Catalyzed Asymmetric Hydrovinylation -- 2.1.5.4.6 Nickel-Catalyzed Cycloisomerization of 1,6-Dienes -- 2.1.5.5 Conclusions -- 2.1.6 Immobilization of Transition Metal Complexes and Their Application to Enantioselective Catalysis -- 2.1.6.1 Introduction -- 2.1.6.2 Immobilized Rh Diphosphino Complexes as Catalysts for Asymmetric Hydrogenation -- 2.1.6.2.1 Preparation and Characterization of the Immobilized Rh-Diphosphine Complexes -- 2.1.6.2.2 Enantioselective Hydrogenation over Immobilized Rhodium Diphosphine Complexes -- 2.1.6.3 Heterogeneous Asymmetric Epoxidation of Olefins over Jacobsen's Catalyst Immobilized in Inorganic Porous Materials -- 2.1.6.3.1 Preparation and Characterization of Immobilized Jacobsen's Catalysts -- 2.1.6.3.2 Epoxidation of Olefins over Immobilized Jacobsen Catalysts -- 2.1.6.4 Novel Heterogenized Catalysts for Asymmetric Ring-Opening Reactions of Epoxides -- 2.1.6.4.1 Synthesis and Characterization of the Heterogenized Catalysts -- 2.1.6.4.2 Asymmetric Ring Opening of Epoxides over New Heterogenized Catalysts -- 2.1.6.5 Conclusions -- 2.2 Biological Methods -- 2.2.1 Directed Evolution to Increase the Substrate Range of Benzoylformate Decarboxylase from Pseudomonas putida -- 2.2.1.1 Introduction -- 2.2.1.2 Materials and Methods -- 2.2.1.2.1 Reagents -- 2.2.1.2.2 Construction of Strains for Heterologous Expression of BFD and BAL -- 2.2.1.2.3 Polymerase Chain Reactions -- 2.2.1.2.4 Generation of a BFD Variant Library by Random Mutagenesis -- 2.2.1.2.5 High-Throughput Screening for Carboligation Activity with the Substrates Benzaldehyde and Dimethoxyacetaldehyde -- 2.2.1.2.6 Expression and Purification of BFD Variants -- 2.2.1.2.7 Protein Analysis Methods -- 2.2.1.2.8 Enzyme Activity Assays. , 2.2.1.3 Results and Discussion.

Note: Cover -- Title Page -- Copyright -- Contents -- List of Contributors -- Foreword -- Preface -- Chapter 1 Definitions and Classifications of MBFTs -- 1.1 Introduction -- 1.2 Definitions -- 1.3 Conclusion and Outlook -- References -- Part I Stereoselective Synthesis of Heterocycles -- Chapter 2 Five-Membered Heterocycles -- 2.1 Introduction -- 2.2 Monocyclic Targets -- 2.2.1 1,3-Dipolar Cycloaddition -- 2.2.2 Michael Addition-Initiated Domino Process -- 2.2.3 Multicomponent Reactions -- 2.2.4 Carbohalogenation Reactions -- 2.2.5 Radical Processes -- 2.3 Fused Polycyclic Targets -- 2.3.1 Cycloaddition Reactions -- 2.3.2 Domino Cyclization Reactions -- 2.4 Bridged Polycyclic Targets -- 2.5 Conclusion and Outlook -- References -- Chapter 3 Six-Membered Heterocycles -- 3.1 Introduction -- 3.2 Monocyclic Targets -- 3.2.1 Nitrogen-Only Heterocycles -- 3.2.2 Oxygen-Containing Heterocycles -- 3.3 Fused Polycyclic Targets -- 3.3.1 Nitrogen-Only Fused Polycyclic Targets -- 3.3.2 Oxygen-Containing Fused Polycyclic Targets -- 3.3.3 Sulfur-Containing Fused Polycyclic Targets -- 3.4 Bridged Polycyclic Targets -- 3.4.1 General Procedure for the Preparation of 2,6-DABCO-Derived Compounds 138 -- 3.5 Polycyclic Spiro Targets -- 3.6 Summary and Outlook -- References -- Chapter 4 Other Heterocycles -- 4.1 Introduction -- 4.2 Synthesis of Medium-Sized Monocyclic, Fused and Bridged Polycyclic Heterocycles -- 4.2.1 Ring Synthesis by Ring Transformation via Rearrangements/Ring Expansions -- 4.2.2 Ring Synthesis by Annulation -- 4.3 Summary and Outlook -- References -- Part II Stereoselective Synthesis of Carbocycles -- Chapter 5 Three- and Four-Membered Carbocycles -- 5.1 Introduction -- 5.2 Cyclopropane Derivatives -- 5.2.1 Organocatalysis and Related Reactions [Michael-Initiated Ring-Closure (MIRC) Reactions] -- 5.2.2 Organometallics and Metal Catalysis. , 5.2.3 Lewis Acid-Promoted Sequences -- 5.2.4 Pericyclic Domino Strategies -- 5.2.5 Radical Domino Strategies -- 5.3 Cyclobutane Derivatives -- 5.3.1 Organocatalyzed Cyclobutanations -- 5.3.2 Organometallics and Metal Catalysis -- 5.3.3 Acid- or Base-Promoted Transformations -- 5.3.4 Multicomponent Reactions (MCRs) -- 5.4 Summary and Outlook -- References -- Chapter 6 Five-Membered Carbocycles -- 6.1 Introduction -- 6.2 Monocyclic Targets -- 6.2.1 Metal-Catalyzed Reactions -- 6.2.2 Organocatalytic Reactions -- 6.2.3 Miscellaneous Reactions -- 6.3 Fused Polycyclic Targets -- 6.3.1 Metal-Catalyzed Reactions -- 6.3.2 Organocatalytic Reactions -- 6.3.3 Lewis Acid-Catalyzed Reactions -- 6.3.4 Miscellaneous Reactions -- 6.4 Bridged Polycyclic Targets -- 6.5 Conclusion and Outlook -- References -- Chapter 7 Stereoselective Synthesis of Six-Membered Carbocycles -- 7.1 Introduction -- 7.2 Metal-Catalyzed Stereoselective Multiple Bond-Forming Transformations -- 7.2.1 Introduction -- 7.2.2 Cycloadditions -- 7.2.3 Metal-Catalyzed Cascades as Formal [2+2+2] Cycloadditions -- 7.2.4 Metal-Catalyzed Cycloisomerization Cascades -- 7.3 Enantioselective Organocatalyzed Synthesis of Six-Membered Rings -- 7.3.1 Organocatalyzed Miscellaneous Reactions -- 7.3.2 Organocatalyzed Cascade and Multicomponent Reactions -- 7.3.3 Polycyclization Cascade Reactions -- 7.4 Stereoselective Multiple Bond-Forming Radical Transformations -- 7.4.1 Intermolecular Cascade Reactions -- 7.4.2 Intramolecular Cascade Reactions -- 7.5 Conclusions -- References -- Chapter 8 Seven- and Eight-Membered Carbocycles -- 8.1 Introduction -- 8.2 Cycloheptenes -- 8.3 Cycloheptadienes -- 8.4 Cycloheptatrienes -- 8.5 Cyclooctenes -- 8.6 Cyclooctadienes -- 8.7 Cyclooctatrienes -- 8.8 Cyclooctatetraenes -- 8.9 Concluding Remarks -- References -- Part III Stereoselective Synthesis of Spirocyclic Compounds. , Chapter 9 Metal-Assisted Methodologies -- 9.1 Introduction -- 9.2 Quaternary Spirocenter -- 9.2.1 Copper-Assisted Methodologies -- 9.2.2 Gold-Assisted Methodologies -- 9.2.3 Palladium-Assisted Methodologies -- 9.2.4 Rhodium-Assisted Methodologies -- 9.2.5 Platinum-Assisted Methodologies -- 9.3 α-Heteroatom-Substituted Spirocenter -- 9.3.1 Zinc-, Magnesium-, and Copper-Assisted Methodologies -- 9.3.2 Titanium-Assisted Methodologies -- 9.3.3 Gold- and Platinum-Assisted Methodologies -- 9.3.4 Palladium-Assisted Methodologies -- 9.3.5 Rhodium-Assisted Methodologies -- 9.4 α,α'-Diheteroatom-Substituted Spirocenter -- 9.5 Conclusion and Outlook -- References -- Chapter 10 Organocatalyzed Methodologies -- 10.1 Introduction -- 10.2 Enantioselective Synthesis of All-Carbon Spirocenters -- 10.2.1 Organocatalytic Enantioselective Methodologies for the Synthesis of Spirooxindoles -- 10.2.2 Other Spirocycles -- 10.3 Enantioselective Synthesis Spirocenters with at Least One Heteroatom -- 10.3.1 Synthesis of Spirooxindoles -- 10.3.2 Synthesis of Other Spirocycles -- 10.4 Conclusion and Outlook -- References -- Part IV Stereoselective Synthesis of Acyclic Compounds -- Chapter 11 Metal-Catalyzed Methodologies -- 11.1 Introduction -- 11.2 Anion Relay Approach -- 11.3 Mannich Reaction -- 11.3.1 Diastereoselective Approach -- 11.3.2 Enantioselective Approach -- 11.4 Reactions Involving Isonitriles -- 11.4.1 Diastereoselective Passerini Reaction -- 11.4.2 Enantioselective Passerini Reaction -- 11.4.3 Diastereoselective Ugi Reaction -- 11.5 1,2-Addition-Type Processes -- 11.5.1 Diastereoselective Approach -- 11.5.2 Enantioselective Approach -- 11.6 Michael-Type Processes -- 11.6.1 Diastereoselective Approach -- 11.6.2 Enantioselective Approach -- 11.7 Summary and Outlook -- References -- Chapter 12 Organocatalyzed Methodologies -- 12.1 Introduction -- 12.2 Aminocatalysis. , 12.2.1 Enamine-Enamine Activation -- 12.2.2 Iminium-Enamine Activation -- 12.3 N-Heterocyclic Carbene (NHC) Activation -- 12.4 H-Bonding Activation -- 12.5 Phase-Transfer Catalysis -- 12.6 Summary and Outlook -- References -- Part V Multiple Bond-Forming Transformations: Synthetic Applications -- Chapter 13 MBFTs for the Total Synthesis of Natural Products -- 13.1 Introduction -- 13.2 Anionic-Initiated MBFTs -- 13.3 Cationic-Initiated MBFTs -- 13.4 Radical-Mediated MBFTs -- 13.5 Pericyclic MBFTs -- 13.6 Transition-Metal-Catalyzed MBFTs -- 13.7 Summary and Outlook -- References -- Chapter 14 Synthesis of Biologically Relevant Molecules -- 14.1 Introduction -- 14.2 Organocatalyzed MBFTs for BRMs -- 14.3 Multicomponent MBFTs for BRMs -- 14.4 Palladium-Catalyzed MBFTs for BRMs -- 14.5 Conclusion and Outlook -- References -- Chapter 15 Industrial Applications of Multiple Bond-Forming Transformations (MBFTs) -- 15.1 Introduction -- 15.2 Applications of MBFTs -- 15.2.1 Xylocaine -- 15.2.2 Almorexant -- 15.2.3 (-)-Oseltamivir (Tamiflu®) -- 15.2.4 Telaprevir (Incivek®) -- 15.2.5 Ezetimibe (Zetia®) -- 15.2.6 Crixivan (Indinavir®) -- 15.2.7 Oxytocine Antagonists: Retosiban and Epelsiban -- 15.2.8 Praziquantel (Biltricide®) -- 15.3 Summary and Outlook -- References -- Index -- EULA.