Catalytic Asymmetric Synthesis

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7 PART I: ASYMMETRIC ORGANOCATALYSIS 1 ASYMMETRIC ENAMINE AND IMINIUM ION CATALYSIS 1.1. INTRODUCTION 1.2. REPRESENTATIVE ORGANOCATALYSTS 1.3. ENAMINE 1.4. IMINIUM ION 1.5. DOMINO REACTION 1.6. DOMINO REACTION AND TOTAL SYNTHESIS 1.7. COMBINATION OF TWO CATALYSTS 1.8. CONCLUSION REFERENCES 2 ASYMMETRIC ACID ORGANOCATALYSIS 2.1. INTRODUCTION 2.2. FEATURES OF CHIRAL BRØNSTED ACIDS 2.3. NUCLEOPHILIC REACTIONS 2.4. CYCLOADDITION REACTIONS 2.5. MICHAEL REACTIONS 2.6. REDUCTION 2.7. ADDITION TO ALKENES 2.8. SUBSTITUTION REACTIONS 2.9. REARRANGEMENT REACTIONS 2.10. MISCELLANEOUS REACTIONS 2.11. CONSTRUCTION OF AXIALLY, PLANAR, AND HELICALLY CHIRAL COMPOUNDS 2.12. COMBINATION WITH TRANSITION METAL CATALYSTS [25–27] 2.13. COMBINATION WITH PHOTOREDOX CATALYST 2.14. CONCLUSION ACKNOWLEDGMENTS REFERENCES 3 ASYMMETRIC BASE ORGANOCATALYSIS 3.1. INTRODUCTION 3.2. CHIRAL TERTIARY AMINE CATALYSTS: CHIRAL ACID–BASE BIFUNCTIONAL CATALYSIS 3.3. CHIRAL GUANIDINE CATALYSTS 3.4. OTHER CHIRAL UNCHARGED ORGANOBASE CATALYSTS: CHIRAL ORGANOSUPERBASES 3.5. CONCLUSION AND OUTLOOK REFERENCES 4 ASYMMETRIC PHASE‐TRANSFER AND ION‐PAIR ORGANOCATALYSES 4.1. INTRODUCTION 4.2. CHIRAL CATION 4.3. CHIRAL‐ANION 4.4. CONCLUSION REFERENCES 5 ASYMMETRIC PEPTIDE CATALYSIS 5.1 INTRODUCTION 5.2 CATALYSIS BY N‐TERMINAL AMINO GROUP OF PEPTIDES 5.3 CATALYSIS BY SIDE CHAIN FUNCTIONAL GROUP ON PEPTIDES 5.4 CATALYSIS BY FUNCTIONAL GROUPS COVALENTLY BOUND TO PEPTIDES 5.5 PEPTIDE CATALYSIS WITH OTHER TYPES OF CATALYTIC CENTERS 5.6 CONCLUSION REFERENCES 6 ASYMMETRIC CARBENE CATALYSIS 6.1. EARLY DEVELOPMENT OF ASYMMETRIC NHC CATALYSIS 6.2. ACTIVATION OF SUBSTRATES BEYOND ALDEHYDES 6.3. SINGLE‐ELECTRON TRANSFER ACTIVATION AND RADICAL REACTIONS 6.4. NHC AS NON‐COVALENT (BRØNSTED BASE) CATALYSTS 6.5. COOPERATIVE CATALYSIS OF NHCs WITH OTHER CATALYSTS 6.6. SYNTHETIC APPLICATIONS OF NHC CATALYSIS 6.7. SUMMARY AND OUTLOOK REFERENCES 7 ASYMMETRIC HYPERVALENT IODINE CATALYSIS 7.1 INTRODUCTION 7.2 OXIDATIVE DEAROMATIVE COUPLING OF ARENOLS 7.3 OXIDATIVE α‐FUNCTIONALIZATION OF CARBONYL COMPOUNDS 7.4 OXIDATIVE DIFUNCTIONALIZAITON OF ALKENES 7.5 CONCLUSION AND OUTLOOK REFERENCES

8 PART II: ASYMMETRIC PHOTOCHEMICAL REACTIONS AND PHOTOREDOX CATALYSIS 8 ASYMMETRIC VISIBLE‐LIGHT PHOTOREDOX CATALYSIS 8.1. INTRODUCTION 8.2. DUAL CATALYSIS APPROACH 8.3. SINGLE BIFUNCTIONAL CATALYST APPROACH 8.4. CONCLUSION REFERENCES 9 ASYMMETRIC PHOTOREDOX REACTIONS WITHOUT PHOTOCATALYSTS 9.1. GENERAL INTRODUCTION 9.2 PHOTOEXCITATION OF ORGANOCATALYTIC INTERMEDIATES 9.3 PHOTOEXCITATION OF METAL‐BASED INTERMEDIATES 9.4 PHOTOCHEMISTRY AND BIOCATALYSIS 9.5 METHODS BASED ON THE DIRECT EXCITATION OF SUBSTRATES 9.6 CONCLUSIONS ACKNOWLEDGMENTS REFERENCES 10 ENANTIOSELECTIVE PHOTOCHEMICAL [2+2] CYCLOADDITION REACTIONS 10.1. INTRODUCTION 10.2. CHIRAL ORGANOCATALYSTS 10.3. CHIRAL METAL CATALYSTS 10.4. DUAL CATALYSIS 10.5. CHIRAL METAL‐ORGANIC CAGES 10.6. CONCLUDING REMARKS ACKNOWLEDGMENTS REFERENCES

9 PART III: ASYMMETRIC SYNTHESIS THROUGH C–H BOND ACTIVATION 11 ASYMMETRIC C–H FUNCTIONALIZATION OF C(sp 2)–H BOND 11.1. INTRODUCTION 11.2. PALLADIUM CATALYSIS 11.3. RHODIUM CATALYSIS 11.4. IRIDIUM CATALYSIS 11.5. RUTHENIUM CATALYSIS 11.6. SCANDIUM CATALYSIS 11.7. NICKEL CATALYSIS 11.8. COBALT CATALYSIS 11.9. COPPER CATALYSIS 11.10. IRON CATALYSIS 11.11. CONCLUSIONS ACKNOWLEDGMENTS REFERENCES 12 ASYMMETRIC C–H FUNCTIONALIZATION OF C(sp 3)–H BOND 12.1. INTRODUCTION 12.2. C(sp 3)–H BOND INSERTION BY METAL CARBENOIDS AND METAL NITRENOIDS 12.3. CONCERTED METALATION‐DEPROTONATION FOR ASYMMETRIC C(sp 3)–H ACTIVATION 12.4. C(sp 3)–H ACTIVATION VIA OXIDATIVE ADDITION MECHANISM 12.5. CONCLUSION REFERENCES

10 PART IV: ASYMMETRIC SYNTHESIS THROUGH CARBON–HALOGEN BOND FORMATION AND ENZYME CATALYSIS 13 ASYMMETRIC CARBON–HALOGEN BOND FORMING REACTIONS (EXCLUDING C–H ACTIVATION PROCESSES) 13.1. INTRODUCTION 13.2. ASYMMETRIC C–F BOND FORMATION WITH METAL CATALYSTS 13.3. ASYMMETRIC C–F BOND FORMING REACTIONS USING CHIRAL PHASE TRANSFER CATALYSIS 13.4. ASYMMETRIC ORGANOCATALYTIC FORMATION OF C–F BONDS 13.5. ASYMMETRIC FORMATION OF C–F BONDS VIA MISCELLANEOUS REACTIONS 13.6. ENANTIOSELECTIVE CHLORINATION 13.7. ENANTIOSELECTIVE BROMINATION 13.8. ASYMMETRIC CARBON–IODINE BOND FORMATION 13.9. CONCLUSIONS ACKNOWLEDGMENTS REFERENCES 14 ENZYME‐CATALYZED ASYMMETRIC SYNTHESIS 14.1. TYPES OF BIOCATALYZED PROCESSES 14.2. KINETIC RESOLUTION 14.3. DYNAMIC PROCESSES IN BIOCATALYZED ASYMMETRIC SYNTHESIS 14.4. DERACEMIZATIONS 14.5. PARALLEL KINETIC RESOLUTIONS 14.6. DESYMMETRIZATION 14.7. MULTI(CHEMO)ENZYMATIC REACTIONS 14.8. CONCLUSIONS AND OUTLOOK REFERENCES

11 PART V: ASYMMETRIC HYDROGENATION 15 ASYMMETRIC HYDROGENATION 15.1. INTRODUCTION 15.2. ASYMMETRIC HYDROGENATION OF FUNCTIONALIZED OLEFINS 15.3. ASYMMETRIC HYDROGENATION OF UNFUNCTIONALIZED OLEFINS 15.4. ASYMMETRIC HYDROGENATION OF KETONES 15.5. ASYMMETRIC HYDROGENATION OF IMINES 15.6. CONCLUSIONS REFERENCES

12 PART VI: ASYMMETRIC CARBON–CARBON BOND FORMING REACTIONS CHAPTER 16 ASYMMETRIC NUCLEOPHILIC ADDITION TO KETONES AND KETIMINES AND CONJUGATE ADDITION REACTIONS 16.1. INTRODUCTION 16.2. ASYMMETRIC NUCLEOPHILIC ADDITION TO KETONES 16.3. ASYMMETRIC NUCLEOPHILIC ADDITION TO KETIMINES 16.4. CATALYTIC ASYMMETRIC CONJUGATE ADDITION 16.5. CONCLUSIONS ACKNOWLEDGMENTS REFERENCES 17 ASYMMETRIC ALLYLIC ALKYLATION, ALLYLATION, AND RELATED REACTIONS 17.1. INTRODUCTION AND SCOPE 17.2. PALLADIUM‐CATALYZED ENANTIOSELECTIVE ALLYLIC ALKYLATIONS 17.3. NICKEL‐ AND PLATINUM‐CATALYZED ALLYLIC ALKYLATION 17.4. MOLYBDENUM‐ AND TUNGSTEN‐CATALYZED ENANTIOSELECTIVE ALLYLIC ALKYLATION 17.5. IRON‐ AND RUTHENIUM‐CATALYZED ALLYLIC ALKYLATION 17.6. RHODIUM‐CATALYZED ENANTIOSELECTIVE ALLYLIC ALKYLATION 17.7. IRIDIUM‐CATALYZED ENANTIOSELECTIVE ALLYLIC ALKYLATION 17.8. COPPER‐CATALYZED ENANTIOSELECTIVE ALLYLIC ALKYLATION 17.9. COBALT‐CATALYZED ENANTIOSELECTIVE ALLYLIC ALKYLATION 17.10. CONCLUDING REMARKS REFERENCES 18 ASYMMETRIC CARBOMETALLATIONS INCLUDING CARBOCYCLIZATIONS 18.1. INTRODUCTION 18.2. CARBOMETALLATIONS WITH MAIN GROUP METALS 18.3. CARBOMETALLATIONS WITH TRANSITION METALS 18.4. CONCLUSION REFERENCES

13 PART VII: ASYMMETRIC SYNTHESIS OF NON‐CENTRO‐CHIRAL COMPOUNDS 19 ASYMMETRIC SYNTHESIS OF AXIALLY CHIRAL COMPOUNDS 19.1. INTRODUCTION 19.2. METAL CATALYSIS 19.3. ORGANOCATALYSIS 19.4. ENZYMATIC CATALYSIS 19.5. CONCLUSION REFERENCES 20 ASYMMETRIC SYNTHESIS OF PLANAR CHIRAL AND HELICALLY CHIRAL COMPOUNDS 20.1. INTRODUCTION 20.2. ENANTIOSELECTIVE SYNTHESIS OF PLANAR CHIRAL COMPOUNDS 20.3. ENANTIOSELECTIVE SYNTHESIS OF HELICALLY CHIRAL COMPOUNDS 20.4. SUMMARY REFERENCES

14 PART VIII: ASYMMETRIC POLYMERIZATION 21 ASYMMETRIC POLYMERIZATION 21.1 INTRODUCTION 21.2 ENANTIOSELECTIVE POLYMERIZATION 21.3 HELIX‐SENSE‐SELECTIVE POLYMERIZATIONS 21.4 SUMMARY AND OUTLOOK REFERENCES

15 PART IX: ASYMMETRIC CATALYSIS IN CONTINUOUS‐FLOW SYSTEM 22 CONTINUOUS‐FLOW CHEMISTRY IN CATALYTIC ASYMMETRIC SYNTHESIS 22.1. INTRODUCTION 22.2. OVERVIEW OF CATALYTIC PROCESSES IN FLOW ORGANIC SYNTHESIS 22.3. ENANTIOSELECTIVE C–C BOND‐FORMING REACTIONS THROUGH 1,4‐ADDITION REACTIONS 22.4. ENANTIOSELECTIVE C–C BOND‐FORMING REACTIONS THROUGH 1,2‐ADDITION REACTIONS 22.5. ENANTIOSELECTIVE C–C BOND FORMATION THROUGH CYCLOADDITION REACTIONS 22.6. ENANTIOSELECTIVE C–C BOND‐FORMING REACTIONS THROUGH HYDROFORMYLATION 22.7. ENANTIOSELECTIVE C–X BOND‐FORMING REACTIONS THROUGH OXIDATIVE PROCESSES 22.8. ENANTIOSELECTIVE REDUCTION OF DOUBLE BONDS THROUGH CONTINUOUS‐FLOW SYSTEMS 22.9. CONCLUSION AND OUTLOOK REFERENCES

16 INDEX

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1 Chapter 1 TABLE 1.1. The two reaction paths in the reaction of cinnamaldehyde and cyc...