Stereoselective Synthesis of Drugs And Natural Products -- Volume 1 -- Contents -- Preface -- Contributors -- List of Abbreviations and Acronyms -- Part I: General Methods and Strategies -- 1 Principles, Concepts, and Strategies of Stereoselective Synthesis -- INTRODUCTION -- 1.1. GENERAL PRINCIPLES AND CONCEPTS -- 1.1.1. Concept of Isomerism -- 1.1.2. Constitutional (Structural) Isomers -- 1.1.3. Basic Concepts of Stereochemistry -- 1.2. THE MAIN STRATEGIES TO ACCESS OPTICALLY ACTIVE PRODUCTS -- 1.2.1. Chiral Resolution -- 1.2.2. Chiral Pool (Chiron Approach) -- 1.2.3. Stereoselective Synthesis -- REFERENCES -- 2 Chiral Auxiliaries in Drug Synthesis -- INTRODUCTION -- 2.1. DIASTEREOSELECTIVE ALDOL REACTIONS -- 2.2. DIASTEREOSELECTIVE HYDROGENATION REACTIONS -- 2.3. DIASTEREOSELECTIVE ALKYLATION REACTIONS -- 2.4. DIASTEREOSELECTIVE CHLOROMETHYLATION -- 2.5. DIASTEREOSELECTIVE CONJUGATE ADDITION REACTIONS -- 2.6. DIASTEREOSELECTIVE ADDITIONS TO IMINES -- 2.7. DIASTEREOSELECTIVE ADDITIONS OF TRIFLUOROMETHYL ANION -- 2.8. SUMMARY AND OUTLOOK -- REFERENCES -- 3 Solid-Phase Organic Synthesis of Drugs and Natural Products -- INTRODUCTION -- 3.1. SOLID-PHASE SYNTHESIS OF ALKALOIDS -- 3.2. SOLID-PHASE SYNTHESIS OF ANTIBIOTICS -- 3.2.1. Strategies for the Solid-Phase Synthesis of β-lactam Antibiotics and Related Compounds -- 3.2.2. Solid-phase Synthesis of Other Antibiotics -- 3.3. SOLID-PHASE SYNTHESIS OF OLIGOSACCHARIDES -- 3.4. SOLID-PHASE SYNTHESIS OF TERPENES, STEROIDS, TERPENOIDS, AND RELATED NATURAL PRODUCTS -- 3.5. SOLID-PHASE SYNTHESIS OF MACROCYCLIC NATURAL PRODUCTS -- 3.6. SOLID-PHASE SYNTHESIS OF OTHER NATURAL PRODUCTS -- 3.6.1. Solid-phase Synthesis of Flavones and Related Compounds -- 3.6.2. Solid-phase Synthesis of Coumarins and Related Compounds -- 3.6.3. Solid-phase Synthesis of Prostaglandins.

3.6.4. Solid-phase Synthesis of Modulators of Protein Kinase C -- 3.7. SUMMARY -- REFERENCES -- 4 Asymmetric Phase-Transfer Catalysis -- INTRODUCTION -- 4.1. ASYMMETRIC PHASE-TRANSFER- CATALYZED ALKYLATION -- 4.1.1. Amino-acid-derived Schiff Bases -- 4.1.2. Carbonyl Compounds Other Than Amino-acid-derived Schiff Bases -- 4.2. ASYMMETRIC PHASE-TRANSFER- CATALYZED C-C BOND FORMATION -- 4.2.1. 1,2-Addition -- 4.2.2. 1,4-Addition -- 4.3. OTHER PHASE-TRANSFER-CATALYZED REACTIONS -- 4.4. GENERAL EXPERIMENTAL GUIDELINES FOR ASYMMETRIC PHASE-TRANSFER REACTIONS -- 4.5. CONCLUSION -- REFERENCES -- 5 Microwave-Assisted Stereoselective Synthesis -- INTRODUCTION -- 5.1. THEORY OF MAOS -- 5.1.1. Background -- 5.1.2. Principles of MAOS -- 5.1.3. Microwaves and Conventional Heating -- 5.2. EQUIPMENT REVIEW -- 5.2.1. Mon omode Instrume nts for Laborato ry-scal e MAOS -- 5.2.2. Monom ode and Multimode Instr uments for largescale Prepara tions -- 5.2.3. Mic rowave- assisted Capillary Cont inuous- Flow Organ ic Syn thesis -- 5.3. MAOS: APPLICATIONS IN STEREOSELECTIVE SYNTHESIS -- 5.3.1. Domino Multicomponent Synthesis of Pentacyclic Oxazinones -- 5.3.2. Diastereoselective Syntheses of a-spiro-d-lactones -- 5.3.3. Diastereoselective Syntheses of a-spiro-d-lactams -- 5.3.4. Diastereoselective Synthesis of Spiro Pyrazolidinones -- 5.3.5. Some Practical Features of the Protocols Described -- 5.4. CONCLUSION -- REFERENCES -- 6 Application of Microreactor Methodology for Organic Synthesis -- INTRODUCTION TO MICROREACTOR TECHNOLOGY -- 6.1. PRACTICAL IMPLICATIONS IN THE DEVELOPMENT OF CONTINUOUS PROCESSES -- 6.2. CHEMICAL SYNTHESIS IN CONTINUOUS FLOW REACTORS -- 6.3. INDUSTRIAL-SCALE APPLICATION OF MICROREACTOR TECHNOLOGY -- 6.4. CONCLUSION -- REFERENCES -- Part II: Stereoselective Synthesis by Bond Formation -- II.1. Stereoselective Methods for C-C Bond Formation.

7 Asymmetric α-Alkylation of Aldehydes, Ketones, and Carboxylic Acids -- INTRODUCTION -- 7.1. ASYMMETRIC α-ALKYLATION OF ALDEHYDES AND KETONES -- 7.1.1. Chiral Auxiliaries -- 7.1.2. Catalytic Methods -- 7.2. ASYMMETRIC α-ALKYLATION OF CARBOXYLIC ACIDS -- 7.2.1. Alkylation of Enolates -- 7.2.2. Alkylation of dianions -- 7.3. CONCLUSION AND OUTLOOK -- REFERENCES -- 8 Asymmetric Aldol Reactions in the Total Syntheses of Natural Products -- INTRODUCTION -- 8.1. ASYMMETRIC ALDOL REACTIONS USING THE OXAZOLIDONE CHIRAL AUXILIARY -- 8.2. OTHER TYPES OF ALDOL REACTIONS USING THE CHIRAL OXAZOLIDINONE -- 8.3. BORON-MEDIATED ASYMMETRIC ALDOL REACTIONS FOR THE CONVERGENT SYNTHESIS OF NATURAL PRODUCTS -- 8.4. MUKAIYAMA ALDOL REACTIONS -- 8.5. ALDOL REACTIONS WITH CHIRAL ALDEHYDES -- 8.6. THE DOUBLE STEREODIFFERENTIATION IN ALDOL REACTIONS -- 8.6.1. The Matched Pair and the Mismatched Pair -- 8.7. THE DIRECT CATALYTIC ASYMMETRIC ALDOL REACTIONS -- 8.8. ALDOL REACTIONS WITH ORGANOCATALYSTS -- 8.9. THE ASYMMETRIC VINYLOGOUS MUKAIYAMA ALDOL REACTIONS -- REFERENCES -- 9 Asymmetric Michael Addition and Related Reactions -- INTRODUCTION -- 9.1. CATALYTIC ENANTIOSELECTIVE MICHAEL ADDITION OF 1,3-DICARBONYL COMPOUNDS TO CYCLIC ENONE FOR THE SYNTHESIS OF THE STRYCHNOS ALKALOIDS AND MAGNOLIONE ANALOGS -- 9.1.1. Metal Prolinate -- 9.1.2. Chiral Metal Complexes -- 9.1.3. Organocatalysis -- 9.1.4. Application of Chiral Michael Adducts from Cyclic Enone in the Synthesis of Natural Product and Biologically Active Products -- 9.2. CATALYTIC ENANTIOSELECTIVE MICHAEL ADDITION OF 1,3-DICARBONYL COMPOUNDS TO ACYCLIC ENONE FOR THE SYNTHESIS OF WARFARIN ANTICOAGULANTS IN ONE STEP -- 9.2.1. Demir et al.'s Synthesis: A Chiral Auxiliary Strategy -- 9.2.2. Organocatalytic Asymmetric Michael Addition of 4-Hydroxycoumarin to Enone -- CONCLUSION -- REFERENCES.

10 Construction of Polypropionate Fragments in Natural Product Synthesis -- INTRODUCTION -- 10.1. INSIGHT INTO POLYPROPIONATE BIOSYNTHESIS -- 10.2. SYNTHETIC APPROACHES TO THE POLYPROPIONATE FRAGMENTS -- 10.2.1. Aldol Reactions -- 10.2.2. Allylation and Crotylation -- 10.2.3. Additions of Allenylmetals to Aldehydes -- 10.2.4. Bidirectional Chain Elongation -- 10.2.5. Cycloaddition Reactions in Polypropionate Synthesis -- 10.2.6. Other Methods -- 10.3. SELECTED TOTAL SYNTHESIS OF POLYPROPIONATE NATURAL PRODUCTS -- 10.3.1. Leighton Group's Zincophorin Methyl Ester Synthesis -- 10.3.2. Showcase of Polypropionate Chemistry in R&D: Total Synthesis of (+)-discodermolide by Novartis -- CONCLUSION -- REFERENCES -- 11 Organocatalytic Conjugate Addition in Stereoselective Synthesis -- 11.1. ORGANOCATALYTIC CONJUGATE ADDITION -- 11.2. MODES OF ACTIVATIONS -- 11.3. EXPERIMENTAL ASPECTS -- 11.4. IMINIUM CATALYSIS -- 11.5. ENAMINE CATALYSIS -- 11.6. DIENAMINE CATALYSIS -- 11.7. CASCADE REACTIONS IN THE TOTAL SYNTHESIS OF NATURAL PRODUCTS -- 11.8. BIFUNCTIONAL BRØNSTED BASE/ACID CATALYSIS -- 11.9. PHASE-TRANSFER CATALYSIS -- 11.10. N-HETEREOCYCLIC CARBENES CATALYSIS -- 11.11. CONCLUSION -- REFERENCES -- 12 Stereoselective Nozaki-Hiyama-Kishi Reaction -- INTRODUCTION -- 12.1. DEVELOPMENT OF THE CATALYTIC NHK REACTION -- 12.2. DIASTEREOSELECTIVITY IN REACTIONS WITH MONOSUBSTITUTED ALLYLIC HALIDES -- 12.3. CATALYTIC ENANTIOSELECTIVE NHK REACTION -- 12.4. APPLICATION OF SALEN-DERIVED LIGANDS IN THE ENANTIOSELECTIVE NHK REACTION -- 12.5. OXAZOLINE-CONTAINING LIGANDS IN THE CATALYTIC ENANTIOSELECTIVE NHK REACTION -- 12.6. APPLICATION OF TETHERED BIS(8- QUINOLINATO) CHROMIUM COMPLEXES IN THE CATALYTIC ENANTIOSELECTIVE NHK REACTION -- 12.7. APPLICATION OF CHIRAL SPIROCYCLIC BORATE LIGANDS TO THE CATALYTIC ENANTIOSELECTIVE NHK ALLYLATION.

12.8. APPLICATIONS OF STEREOSELECTIVE NHK REACTION IN TOTAL SYNTHESIS -- 12.9. EXPERIMENTAL PROCEDURES -- 12.10. APPLICATIONS IN NATURAL PRODUCTS SYNTHESIS -- 12.11. CONCLUSIONS -- REFERENCES -- 13 Transition-Metal-Catalyzed Asymmetric C-C Cross-Couplings in Stereoselective Synthesis -- INTRODUCTION -- 13.1. ASYMMETRIC HECK REACTION -- 13.2. ASYMMETRIC SUZUKI-MIYAURA REACTION -- 13.3. ASYMMETRIC SONOGASHIRA REACTION -- 13.4. ASYMMETRIC STILLE REACTION -- 13.5. ASYMMETRIC NEGISHI REACTION -- 13.6. ASYMMETRIC ALLYLIC ALKYLATION -- 13.7. ASYMMETRIC ARYLATION OF KETONES -- 13.8. CONCLUSIONS AND FUTURE PROSPECTS -- REFERENCES -- 14 Asymmetric Hydroformylation, Hydroxycarbonylation, and Alkoxycarbonylation for Stereoselective Synthesis -- 14.1. ASYMMETRIC HYDROFORMYLATION -- 14.1.1. General Considerations: Is a Substrate Suitable for Enantioselective Hydroformylation? -- 14.2. ALKOXYCARBONYLATION AND HYDROXYCARBONYLATION OF ALKENES -- 14.3. PRACTICAL CONSIDERATIONS -- 14.3.1. Catalysts -- 14.3.2. Solvents -- 14.3.3. Pressure -- 14.3.4. Experimental Procedures -- REFERENCES -- 15 Intramolecular Oxycarbonylation in Stereoselective Synthesis -- INTRODUCTION -- 15.1. INTRAMOLECULAR ALKOXYLATIONMETHOXYCARBONYLATION -- 15.2. INTRAMOLECULAR ALKOXYLATIONLACTONIZATION -- 15.3. INTRAMOLECULAR ALKOXYLATIONCARBOXYLATION -- 15.4. INTRAMOLECULAR ALKOXYLATIONKETONYLATION -- 15.5. ASYMMETRIC INTRAMOLECULAR ALKOXYLATION-CARBONYLATION -- 15.6. CONCLUSION -- ACKNOWLEDGMENTS -- REFERENCES -- 16 Stereoselective Cycloaddition Reactions -- INTRODUCTION -- 16.1. [4 + 2] CYCLOADDITION REACTIONS -- 16.1.1. Synthesis of (-)-oseltamivir phosphate (Tamiflu) -- 16.1.2. Synthesis of Dysidiolide Analogs -- 16.1.3. Synthesis of Paracyclophanes -- 16.1.4. Synthesis of C2-C11 Cyclized Cembranoids -- 16.1.5. Synthesis of Carpanone-Like Molecules.

16.1.6. Synthesis of α,β-unsaturated δ-lactones.