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1 Chapter 1Figure 1.1. Representative organocatalysts.Figure 1.2. The reaction of enamines generated from diphenylprolinol silyl e...Figure 1.3. Nucleophilicity and electrophilicity of enamines and iminium ion...Scheme 1.1. Reactions of cinchona alkaloid catalysts.Figure 1.4. Transition state for the aldol reaction catalyzed by proline....Figure 1.5. Transition state of the Mannich reaction.Scheme 1.2. The reaction mechanism of the Michael reaction of aldehyde and n...Figure 1.6. Diarylprolinol silyl ether in this study.Scheme 1.3. The reaction mechanism of the Diels‐Alder reaction.Scheme 1.4. The reaction mechanism of the Michael reaction.Scheme 1.5. The reaction mechanism.Scheme 1.6. Stereodivergent α‐allylation of branched aldehydes using allyl a...Scheme 1.7. Stereodivergent α‐allylation of branched aldehydes using an alky...

2 Chapter 2Figure 2.1. Examples of chiral Brønsted acids.Figure 2.2. pK_a values of chiral Brønsted acids in DMSO by calculation.Figure 2.3. Effect of 3,3′‐substituents of BINOL‐derived phosphoric acid on ...Figure 2.4. Function of chiral phosphoric acid.Figure 2.5. Metal salts of chiral phosphoric acid.Scheme 2.1. Mannich reaction by Akiyama (a), and by Terada (b)Scheme 2.2. Mannich reaction with N‐(2‐hydroxyphenyl)‐imine (a) and with N‐p...Scheme 2.3. Mannich reaction of 2,4‐pentandione and N‐Cbz‐imine.Scheme 2.4. Mannich reaction between bisi‐silyl ketene acetal and silylated ...Scheme 2.5. Pictet‐Spengler reaction between tryptamine and aldehyde (a) (...Scheme 2.6. Addition of thiol.Scheme 2.7. Addition of hydrazone.Scheme 2.8. Polyene cyclization.Scheme 2.9. Friedel‐Crafts alkylation reaction between indoles and imines....Scheme 2.10. Friedel‐Crafts alkylation reaction with ketimines and indoles (...Scheme 2.11. Friedel‐Crafts alkylation reaction between N‐H trifluoromethyla...Scheme 2.12. Friedel‐Crafts alkylation reaction between indole and N‐H trifl...Scheme 2.13. Internal redox reaction.Scheme 2.14. Radical addition to imines.Scheme 2.15. Torgov reaction.Scheme 2.16. Prins cyclization.Scheme 2.17. Intramolecular carbonyl‐ene reaction.Scheme 2.18. Intermolecular carbonyl‐ene reaction.Scheme 2.19. Kinetic resolution of homoaldols.Scheme 2.20. Allylation of aldehyde by allylboronate (a) (), and propary...Figure 2.6. Transition state model of the allylation with allylboronate.Scheme 2.21. Allylation of aldehyde with γ‐silyl boronate.Scheme 2.22. Allylation of aldehydes with α‐vinyl allylboronate.Scheme 2.23. Reaction between di(boryl)butane and aldehyde, leading to the f...Scheme 2.24. Allylation reaction using 9c (a) and 11b,c (b) (Scheme 2.25. Mukaiyama aldol reaction with ketones (a) and ketone selective ...Figure 2.7. Reaction intermediate in the ketone‐selective reaction.Scheme 2.26. Enantioselective synthesis of isoindolinones.Scheme 2.27. Kinetic resolution of 2‐amido benzyl alcohols.Scheme 2.28. Oxa‐Pictet‐Spengler reaction of 2‐arylethanols.Scheme 2.29. Oxa‐Pictet‐Spengler reaction.Scheme 2.30. Oxa‐Pictet‐Spengler reaction between tryptophol and aldehydes....Scheme 2.31. Oxa‐Pictet‐Spengler reaction with ketal.Scheme 2.32. Diels‐Alder reaction.Scheme 2.33. Diels‐Alder reaction by C–H acid.Figure 2.8. Silylium binaphthyl‐allyl‐tetrasulfonate anion intermediate.Scheme 2.34. Diels‐Alder reaction between simple ester and cyclopentadiene c...Scheme 2.35. Diels–Alder reaction between cyclopentadien and enals (a), and ...Scheme 2.36. Redox‐divergent Diels‐Alde reaction leading to dihydronaphthale...Scheme 2.37. Diels‐Alder reaction promoted by Lewis acid‐assisted Brønsted a...Figure 2.9. Lewis acid‐assisted chiral Brønsted acid.Scheme 2.38. Povarov reaction with N‐2‐hydroxyphenyl imine (a) () and N‐...Figure 2.10. Transition state model of the aza‐Diels‐Alder reaction.Scheme 2.39. Intramolecular Povarov reaction of azadiene.Scheme 2.40. Povarov reaction leading to tetrahydroquinoline with two quater...Scheme 2.41. Hetero‐Diels‐Alder reaction between azopyridine carboxylate and...Scheme 2.42. Addition of enamides to ortho‐quinone methide.Scheme 2.43. Cycloaddition reaction between styrenes and aldimines.Figure 2.11. 3 : 1 : 4 Aqua complex of (R)‐8d/Mg/K.Scheme 2.44. [4+2] cycloaddition reaction between vinyl azides and N‐acyl im...Scheme 2.45. Inverse electron‐demand oxa‐Diels‐Alder reaction of ortho‐quino...Scheme 2.46. Enantioselective synthesis of 4‐aryl‐4H‐chromenes.Scheme 2.47. Synergistic rhodium/phosphoric acid catalysis.Scheme 2.48. 1,3‐Dipolar cycloaddition reaction between azomethine ylide and...Scheme 2.49. [3+2] Cycloaddition reaction of isatin‐derived 3‐indolylmethano...Scheme 2.50. Generation of the indolenium ion intermediate.Scheme 2.51. [4+3] Cycloaddition reaction of indolyl alcohol.Scheme 2.52. [3+2] Cycloaddition of 2‐indolylmethanols.Scheme 2.53. [3+3] Cycloaddition of 2‐indolylmethanols.Scheme 2.54. [4+3] Cycloannulation reaction between ortho‐quinone methides a...Scheme 2.55. [4+3] Cycloaddition reaction between furans and oxa‐allyl catio...Scheme 2.56. Nazarov reaction of acyclic divinyl ketones.Scheme 2.57. Nazarov‐type electrocyclization.Scheme 2.58. Tandem Nazarov cyclization semipinacol rearrangement reaction....Scheme 2.59. Michael reaction cyclohexanone and enone (a) and enol catalysis...Scheme 2.60. Aza‐Michael‐addition reactions of pyrazoles.Scheme 2.61. Sulfa‐Michael reaction to nitroalkenes.Scheme 2.62. Friedel‐Crafts alkylation reaction between indole and nitroalke...Scheme 2.63. Friedel‐Crafts alkylation reaction between nitrostyrenes and py...Scheme 2.64. Transfer hydrogenation of ketimines by Hantzsch ester.Figure 2.12. Results of the transfer hydrogenation of ketimines.Figure 2.13. Transition state of the transfer hydrogenation with Hantzsch es...Scheme 2.65. Transfer hydrogenation of benzoxazine using DHPD.Scheme 2.66. Metal‐Brønsted acid cooperative catalysis.Scheme 2.67. Transfer hydrogenation of N‐alkyl ketimines (a) (), reducti...Figure 2.14. Transfer hydrogenation of ketimines by benzothiazoline.Figure 2.15. Results of the transfer hydrogenation of ketimines by benzothia...Figure 2.16. Transition state of the transfer hydrogenation with Hantzsch es...Scheme 2.68. Transfer hydrogenation using indoline as a hydrogen donor (a) (...Scheme 2.69. Reduction of ketones by the combined use of catecholborane.Scheme 2.70. Transfer hydrogenation of chalcone derivatives.Scheme 2.71. Reduction of indolines.Scheme 2.72. Transfer hydrogenation of 1,1‐diarylethenes.Scheme 2.73. Asymmetric spiroacetalization by confined Brønsted acid.Scheme 2.74. Asymmetric spiroacetalization by TRIP.Scheme 2.75. Intramolecular hydroamination of alkenes (a) (), and its ap...Scheme 2.76. Hydroarylation of 1,1‐diarylethenes.Scheme 2.77. Bromocyclization of polyenes.Scheme 2.78. Intramolecular hydroalkoxylation of unactivated alkenes (a) [16...Scheme 2.79. Construction of all‐carbon quaternary stereocenters from indole...Scheme 2.80. Construction of triarylpyrrolylmethanes (a) and diarylindolylpy...Scheme 2.81. Ring expansion reaction of 1,3‐dithianes.Scheme 2.82. Vinylogous Wagner‐Meerwein shift.Scheme 2.83. House‐Meinwald rearrangement.Scheme 2.84. Construction of quaternary stereocenters by Pinacol rearrangeme...Scheme 2.85. Ring‐opening of meso‐aziridines.Scheme 2.86. Enantioselective oxidation of sulfides to sulfoxides.Scheme 2.87. Kinetic resolution of oxiranes by the transformation of oxirane...Scheme 2.88. α‐Allylation of aldehyde.Scheme 2.89. Dual catalysis system of CPA and Ru complex.Scheme 2.90. Cooperative catalysis with CPA and Rh₂(OAc)_4.Scheme 2.91. Cooperative catalysis with CPA and Fe complex.Scheme 2.92. Cooperative catalysis with CPA and Pd(II) complex (a) (), a...Scheme 2.93. Cooperative catalysis with CPA and Rh₂(OAc)₄.

3 Chapter 3Figure 3.1. General catalytic cycle for Brønsted base catalysis.Figure 3.2. Relationship between basicity of uncharged organobases and acidi...Scheme 3.1. Enantioselective addition of aryl thiols to cyclic enones cataly...Figure 3.3. Cinchona alkaloids and derivatives.Figure 3.4. Chiral acid–base bifunctional catalysts.Scheme 3.2. Enantioselective addition of malonates to nitroalkenes catalyzed...Figure 3.5. Proposed mechanism of the bifunctional amine‐thiourea catalyzed ...Scheme 3.3. Enantioselective addition of nitromethane to chalcone derivative...Scheme 3.4. Enantioselective addition of β‐ketoesters to nitroalkenes cataly...Scheme 3.5. Enantioselective addition of β‐ketoesters to nitroalkenes cataly...Figure 3.6. Transition‐state model of Michael addition catalyzed by 1f.Scheme 3.6. Enantioselective addition of pyrazoleamides 3 to nitroalkenes ca...Scheme 3.7. Enantioselective aldol reaction of malonic acid half thioesters Scheme 3.8. Synthesis of oxindoles possessing adjacent tetrasubstituted ster...Scheme 3.9. Enantioselective aldol reaction of fluorinated malonic acid half...Figure 3.7. N‐Heterocyclic compounds used as a pronucleophile.Scheme 3.10. Enantioselective addition of thiazolones 8 to nitroalkenes cata...Scheme 3.11. Enantioselective addition of MAC reagents 11 to enones catalyze...Scheme 3.12. Enantioselective addition of glyoxylate cyanohydrins to imines ...Scheme 3.13. α‐Functionalization of 2‐alkyl azaarene N‐oxides 13. Source: Ba...Scheme 3.14. Enantioselective Michael addition of barbituric acid derivative...Scheme 3.15. Enantioselective cycloetherification via oxa‐Michael addition c...Scheme 3.16. Enantioselective synthesis of spiroketals.Scheme 3.17. Enantioselective synthesis of tetrahydropyrans with two stereog...Scheme 3.18. Enantioselective intramolecular oxa‐Michael addition of α,β‐uns...Scheme 3.19. Enantioselective intramolecular oxa‐Michael addition of in situ...Scheme 3.20. Enantioselective intramolecular aza‐Michael addition of enamine...Scheme 3.21. One‐pot catalytic enantioselective synthesis of 2‐pyrazolines....Scheme 3.22. Enantioselective addition of thioacids to trisubstituted nitroa...Scheme 3.23. Enantioselective addition of thiols to in situ generated ortho‐...Scheme 3.24. Enantioselective Michael/cyclization reaction sequence catalyze...Scheme 3.25. Enantioselective Tamura cyclization catalyzed by 2w.Scheme 3.26. Enantioselective formal [3+2] cycloaddition of cyclopropyl keto...Scheme 3.27. Enantioselective synthesis of benzazocinones. Source: Based on ...Scheme 3.28. Enantioselective synthesis of axially chiral 4‐arylpyridine der...Scheme 3.29. Enantioselective synthesis of atropoisomeric furans based on th...Scheme 3.30. Intramolecular [4+2] cycloaddition between in situ generated vi...Scheme 3.31. Enantioselective Strecker reaction catalyzed by 21. Source: Bas...Scheme 3.32. Enantioselective Strecker reaction catalyzed by 22a.Figure 3.8. Proposed reaction mechanism.Scheme 3.33. Enantioselective protonation catalyzed by 22b.Scheme 3.34. Enantioselective isomerization of 3‐alkynoate catalyzed by 22b....Scheme 3.35. Enantioselective Michael addition of glycine imines to acrylate...Scheme 3.36. Enantioselective reactions of 5H‐oxazol‐4‐ones as a pronucleoph...Scheme 3.37. Enantioselective addition of phenols to nitroalkenes catalyzed ...Scheme 3.38. Solvent‐dependent enantiodivergent Mannich‐type reaction cataly...Scheme 3.39. Enantioselective addition of β‐ketoesters to nitroalkenes catal...Scheme 3.40. Enantioselective reactions catalyzed by 26.Scheme 3.41. Enantioselective α‐hydroxylation of β‐ketoesters catalyzed by 2...Scheme 3.42. Desymmetrization of meso‐aziridines with thiols catalyzed by 28Figure 3.9. Axially chiral guanidine catalysts.Scheme 3.43. Enantioselective reactions of furanones as a pronucleophile cat...Scheme 3.44. Enantioselective amination of β‐dicarbonyl compounds with azodi...Figure 3.10. Chiral cyclopropenimine catalyst.Scheme 3.45. Enantioselective additions of glycine imines catalyzed by 31....Figure 3.11. Mechanistic rationale.Scheme 3.46. Enantioselective [3+2] cycloaddition of glycine imines with 2‐a...Figure 3.12. Chiral bifunctional iminophosphorane (BIMP) catalysts.Scheme 3.47. Enantioselective addition of nitromethane to ketimines catalyze...Scheme 3.48. Enantioselective reactions catalyzed by 32. (a)(b)(c)...Figure 3.13. Chiral P1‐phosphazene catalysts.Scheme 3.49. Enantioselective addition of nitroalkanes and dialkyl phosphite...Figure 3.14. Proposed transition‐state model.Scheme 3.50. Enantioselective Michael addition reactions catalyzed by (P)‐34Scheme 3.51. Enantioselective aldol‐type reaction of α‐hydroxy phosphonoacet...Scheme 3.52. Enantioselective Payne‐type oxidation of N‐sulfonyl imines cata...Figure 3.15. Chiral higher‐order phosphazene catalysts.Scheme 3.53. Enantioselective amination of 2‐alkyltetralone with azodicarbox...Scheme 3.54. Enantioselective addition reactions of less acidic pronucleophi...Scheme 3.55. Enantioselective formal [3+2] cycloaddition of epoxysulfones wi...Scheme 3.56. Enantioselective direct Mannich‐type reactions catalyzed by chi...

4 Chapter 4Scheme 4.1. Modes of asymmetric phase‐transfer and ion‐pair organocatalysis....Scheme 4.2. First enantioselective alkylation using chiral cation phase tran...Scheme 4.3. Enantioselective benzylation of glycine imines.Scheme 4.4. Catalyst development for the enantioselective mono‐alkylation of...Scheme 4.5. Catalyst development for the enantioselective synthesis α,α...Scheme 4.6. Atropselective enolate O‐alkylation.Scheme 4.7. Enantioselective addition of glycine imines to Michael acceptors...Scheme 4.8. Enantioselective epoxidation of chalcones.Scheme 4.9. Enantioselective aziridination of α,β‐unsaturated esters.Scheme 4.10. Enantioselective aza‐Michael addition of hydrazides to chalcone...Scheme 4.11. Enantioselective aldol reaction using glycine imines.Scheme 4.12. Enantioselective Mannich reaction using glycine imines.Scheme 4.13. Enantioselective arylation of 1,3‐dicarbonyl nucleophiles via n...Scheme 4.14. Enantioselective arylation of mono‐alkylated glycine imines via...Scheme 4.15. Enantioselective arylation of oxindoles via nucleophilic aromat...Scheme 4.16. Atropselective synthesis of biaryl motifs via nucleophilic arom...Scheme 4.17. Atropselective macrocyclization via nucleophilic aromatic subst...Scheme 4.18. Enantioselective α‐fluorination of β‐ketoesters.Scheme 4.19. Enantioselective α‐chlorination and α‐sulfenylation of 1,3‐dica...Scheme 4.20. Enantioselective α‐hydroxylation of indanones.Scheme 4.21. Enantioselective α‐hydroxylation of oxindoles.Scheme 4.22. Enantioselective α‐amination of β‐ketoesters using azodicarboxy...Scheme 4.23. Enantioselective α‐amination of oxindoles and lactones using az...Scheme 4.24. Enantioselective α‐amination of oxindoles using hydroxylamines....Scheme 4.25. Enantioselective oxidation of sulfides using a peroxomolybdate/...Scheme 4.26. Enantioselective transformations via transition metal/chiral ca...Scheme 4.27. Asymmetric Michael addition via cation binding BINOL‐derived et...Scheme 4.28. Enantioselective Michael addition via cation binding sugar‐deri...Scheme 4.29. Kinetic resolution of silyl‐protected alcohols.Scheme 4.30. Asymmetric Strecker reaction catalyzed by BINOL‐derived crown e...Scheme 4.31. First example of asymmetric counteranion‐directed catalysis....Scheme 4.32. Asymmetric counteranion‐directed catalysis involving iminium io...Scheme 4.33. Asymmetric Mukaiyama aldol reaction catalyzed by a highly acidi...Scheme 4.34. Asymmetric counteranion‐directed catalysis involving stabilized...Scheme 4.35. Asymmetric counteranion‐directed catalysis with unstabilized ox...Scheme 4.36. Trityl cation/ chiral phosphate salt activation of α‐ketoesters...Scheme 4.37. Intramolecular asymmetric counteranion‐directed catalysis with ...Scheme 4.38. Intermolecular asymmetric counteranion‐directed catalysis with ...Scheme 4.39. Enantioselective aziridinium and episulfonium ring‐opening.Scheme 4.40. Asymmetric Diels Alder via photoredox/chiral anion dual catalys...Scheme 4.41. First example of chiral anion phase‐transfer catalysis.Scheme 4.42. Overview of chiral anion phase‐transfer catalyzed fluorination ...Scheme 4.43. Chiral anion phase‐transfer catalyzed fluorination with BINOL‐d...Scheme 4.44. Overview of chiral anion phase‐transfer catalyzed bromination a...Scheme 4.45. Chiral anion phase‐transfer catalyzed diazenation.Scheme 4.46. Asymmetric transformations mediated by oxopiperidinium/chiral a...Scheme 4.47. Asymmetric arylation of benzopyrylium with phenols under phase‐...Scheme 4.48. First example of a transition‐metal/chiral anion catalyzed tran...Scheme 4.49. Asymmetric transformations catalyzed by a Pd/chiral phosphate i...Scheme 4.50. Asymmetric transformations catalyzed by other transition‐metals...Scheme 4.51. Enantioselective acyl‐Pictet‐Spengler reaction enabled by anion...Scheme 4.52. Enantioselective reactions enabled by anion‐binding catalysis p...Scheme 4.53. Kinetic resolution of amines via anion‐binding catalysis.Scheme 4.54. Enantioselective reactions of enol ethers enabled by anion‐bind...Scheme 4.55. Enantioselective dearomatization of heterocycles enabled by ani...Scheme 4.56. Enantioselective transformations catalyzed by BINOL‐derived sil...Scheme 4.57. Asymmetric ring opening of strained heterocycles by anion‐bindi...

5 Chapter 5Figure 5.1 Some “standard” peptide catalysts applied to two or more asymmetr...Scheme 5.1 Poly(amino acid)‐catalyzed asymmetric Michael addition.Scheme 5.2 Polyalanine‐catalyzed asymmetric epoxidation (Juliá–Colonna epoxi...Scheme 5.3 Proline‐catalyzed asymmetric Robinson annulation (Hajos–Parrish‐E...Scheme 5.4 Proline‐catalyzed asymmetric cross aldol reaction.Scheme 5.5 Stereochemical outcome for the peptide‐catalyzed asymmetric cross...Scheme 5.6 Combinatorial approach for screening of peptide catalyst for cros...Scheme 5.7 One‐pot sequential reactions including peptide‐catalyzed asymmetr...Scheme 5.8 Peptide‐catalyzed kinetic resolution of planar chiral ansa cyclop...Scheme 5.9 Peptide‐catalyzed kinetic resolution of aldols via enantiomer dis...Scheme 5.10 Peptide‐catalyzed diastereo‐/enantioselective nitro Michael addi...Scheme 5.11 Peptide‐catalyzed stereoselective nitro Michael addition of alde...Figure 5.2 Structure of diastereo‐/enantioselective nitro Michael adducts; (...Scheme 5.12 Peptide‐catalyzed anti‐diastereoselective and enantioselective n...Scheme 5.13 Peptide‐catalyzed asymmetric α‐amination of aldehydes.Scheme 5.14 Peptide‐catalyzed asymmetric Michael addition of 2‐nitropropane ...Scheme 5.15 Peptide‐catalyzed asymmetric hydride conjugate addition to enals...Scheme 5.16 Asymmetric conjugate additions catalyzed by turn‐helix peptides;...Scheme 5.17 Combinatorial approach for screening of peptide catalyst for Mic...Scheme 5.18 Peptide‐catalyzed asymmetric Michael addition of boronic acids t...Scheme 5.19 Peptide‐catalyzed diastereo‐/enantioselective formation of three...Scheme 5.20 Enantiodivergent Michael addition using peptide catalysts having...Scheme 5.21 Peptide‐catalyzed enantioselective Michael addition of malonate ...Scheme 5.22 (a) Peptide‐catalyzed asymmetric Michael addition of carbon nucl...Scheme 5.23 Tandem Michael addition and asymmetric α‐oxyamination of an enal...Scheme 5.24 Divergence in enantioselectivity for catalytic asymmetric epoxid...Figure 5.3 (a) Possible reaction intermediate for Juliá‐Colonna epoxidation....Scheme 5.25 Polyleucine‐catalyzed asymmetric cyanosilylation.Scheme 5.26 Kinetic resolution in the hydrolysis of activated esters by pept...Scheme 5.27 Asymmetric hydrocyanation catalyzed by a cyclic dipeptide.Scheme 5.28 Peptide‐catalyzed kinetic resolution in the acylation of seconda...Scheme 5.29 Combinatorial approach for screening of peptide catalyst for acy...Scheme 5.30 Peptide‐catalyzed enantio‐ or regiodifferentiating reaction in t...Scheme 5.31 Peptide‐catalyzed acylative desymmetrization of a bisphenol‐type...Scheme 5.32 Peptide‐catalyzed site‐selective acylation of a glycoside.Figure 5.4 Site selectivity for the peptide‐catalyzed derivatization of natu...Scheme 5.33 Peptide‐catalyzed acylative kinetic resolution of secondary thio...Scheme 5.34 Peptide‐catalyzed monoacylative kinetic resolution of trans‐cycl...Scheme 5.35 Peptide‐catalyzed monoacylative desymmetrization of alkane‐1,2‐d...Scheme 5.36 Peptide‐catalyzed asymmetric Dakin–West reaction.Scheme 5.37 Peptide‐catalyzed phosphorylative desymmetrization of a myo‐inos...Figure 5.5 Site selectivity for the peptide‐catalyzed phosphorylation of tei...Scheme 5.38 Peptide‐catalyzed sulfonylative desymmetrization of a myo‐inosit...Scheme 5.39 Peptide‐catalyzed site‐selective derivatization of a polyol comp...Scheme 5.40 Peptide/proline‐cocatalyzed asymmetric Morita–Baylis–Hillman rea...Scheme 5.41 Peptide‐catalyzed asymmetric conjugate addition of azide.Scheme 5.42 Catalytic cycle for oxidation mediated by Asp‐containing peptide...Scheme 5.43 Peptide‐catalyzed asymmetric epoxidation of allylic carbamates....Scheme 5.44 Peptide‐catalyzed site‐/enantioselective epoxidation of farnesol...Scheme 5.45 Peptide‐catalyst‐controlled site‐/enantioselective Beayer–Villig...Scheme 5.46 Peptide‐catalyst‐controlled N‐oxidative desymmetrization of dipy...Scheme 5.47 Peptide‐catalyzed N‐Oxidation of conformationally dynamic substr...Scheme 5.48 Peptide‐catalyzed methanolytic dynamic kinetic resolution of oxa...Scheme 5.49 Peptide‐catalyzed asymmetric synthesis of axially chiral bipheny...Scheme 5.50 Peptide‐catalyzed asymmetric synthesis of axially chiral arylami...Scheme 5.51 Peptide‐catalyzed enantioselective synthesis of 3‐arylquinazolin...Scheme 5.52 Peptide‐catalyzed asymmetric synthesis of chiral biaryls by frag...Scheme 5.53 Peptide‐catalyzed asymmetric hydrocyanation of imines by cyclic ...Scheme 5.54 Peptide‐catalyzed asymmetric Michael addition of prochiral nucle...Scheme 5.55 Peptide‐catalyzed atroposelective formation of two‐axis terpheny...Scheme 5.56 Enantioselective Rauhut–Currier reactions promoted by protected ...Scheme 5.57 Enantioselective vinylcyclopropane ring‐opening/cycloaddition ca...Scheme 5.58 Photo‐driven deracemization of urea derivative promoted by a com...Scheme 5.59 Catalytic asymmetric epoxidation of alkenes mediated by trifluor...Scheme 5.60 Peptide‐catalyzed ring‐opening desymmetrization of epoxide.Scheme 5.61 Peptide‐catalyzed acylative kinetic resolution of secondary alco...Scheme 5.62 Peptide‐catalyzed asymmetric bromolaconization.Scheme 5.63 Catalytic oxidation by flavin‐conjugated peptide; (a) sulfoxidat...Scheme 5.64 TEMPO‐conjugated peptoid‐catalyzed oxidative kinetic resolution ...Scheme 5.65 Asymmetric reduction of quinoline derivatives catalyzed by a pep...Scheme 5.66 Reductive kinetic resolution of imines catalyzed by a peptide wi...Scheme 5.67 Enantioselective Baeyer‐Villiger oxidation controlled by a pepti...Scheme 5.68 Atroposelective cyclodehydration leading to axially chiral benzi...Scheme 5.69 Diastereodivergent construction P(III) chiral center from phosph...Scheme 5.70 (a) Pyridine‐conjugated peptide‐catalyzed asymmetric aza‐MBH rea...Scheme 5.71 Site‐selective acylation using peptide catalyst with DMAP‐type s...Scheme 5.72 Peptide‐catalyzed enantioselective transamination of pyruvate....Scheme 5.73 Asymmetric reactions catalyzed by a peptide having thiazolium si...Scheme 5.74 Asymmetric cathodic reduction on polyvaline‐coated graphite elec...Scheme 5.75 Asymmetric anodic sulfoxidation on polyvaline‐coated Pt electrod...

6 Chapter 6Figure 6.1. General structural features of NHCs.Figure 6.2. Early development of benzoin and related reactions via acyl anio...Figure 6.3. Reactions of enals with ketones and aldehydes. (a) NHC‐Catalyzed...Figure 6.4. Reactions of enals with imines, ketimines, and Michael acceptors...Figure 6.5. Reactions of enals involving NHC‐bound enolate intermediates. (a...Figure 6.6. Activation of enals under oxidative NHC catalysis. (a) Generatio...Figure 6.7. NHC‐catalyzed reactions of α‐functionalized aldehydes. (a) Bode’...Figure 6.8. α‐Carbon activation of stable carboxylic esters.Figure 6.9. β‐sp²‐Carbon activation of α,β‐unsaturared carboxylic esters....Figure 6.10. γ‐Carbon activation of α,β‐unsaturared carboxylic esters.Figure 6.11. NHC‐catalyzed β‐activation of carboxylic esters. (a) Chi’s NHC‐...Figure 6.12. NHC‐catalyzed activation of ketenes. (a) NHC‐catalyzed Stauding...Figure 6.13. NHC‐catalyzed activation of sulfonylimines. (a) Hou’s NHC‐catal...Figure 6.14. NHC‐catalyzed umpolung of imines.Figure 6.15. NHC‐catalyzed activation of remote nitrogen atoms.Figure 6.16. NHC‐catalyzed β‐alkylations of Michael acceptors.Figure 6.17. Biomimetic NHC‐catalyzed oxidations of aldehydes.Figure 6.18. NHC‐catalyzed reductive β,β‐coupling of nitroalkenes. (a) Chi’s...Figure 6.19. NHC‐catalyzed reductive coupling of nitrobenzyl bromides.Figure 6.20. Enantioselective β‐hydroxylation of enals via SET processes.Figure 6.21. NHC‐catalyzed alkylation of aldehydes via SET process. (a) NHC‐...Figure 6.22. NHC‐catalyzed SET difunctionalization of olefins.Figure 6.23. Synergistic Ru‐photoredox/NHC catalysis. (a) Ye’s NHC/photoredo...Figure 6.24. Photoredox and carbene catalysis for the generation of ketones....Figure 6.25. Photoenolization/Diels–Alder reaction of acid fluorides.Figure 6.26. NHC‐catalyzed amidation of unactivated esters. (a) NHC‐catalyze...Figure 6.27. Activation of esters and ketones by NHC as Brønsted base. (a) N...Figure 6.28. Michael additions catalyzed by NHCs through non‐covalent pathwa...Figure 6.29. NHC as Brønsted base catalyzed Michael additions. (a) Scheidt’s...Figure 6.30. Early researches on cooperative NHC/Pd catalysis. (a) Hamada’s ...Figure 6.31. NHC/Pd dual‐catalyzed reactions of aldehydes. (a) Liu’s Pd‐NHC ...Figure 6.32. NHC/Pd dual catalyzed asymmetric coupling reactions. (a) NHC/Pd...Figure 6.33. NHC/Pd dual catalyzed umpolung 1,4‐addition.Figure 6.34. NHC/Cu dual‐catalyzed activation of alkynes as enolate equivale...Figure 6.35. NHC/Cu dual‐catalyzed enantioselective [3+3] and [3+4] annulati...Figure 6.36. Kinetic resolution of aziridines enabled by NHC/Cu dual catalys...Figure 6.37. NHC/Au dual‐catalyzed enantioselective annulation reactions....Figure 6.38. NHC/Ir dual‐catalyzed [3+2] and [4+2] annulations. (a) NHC/Ir d...Figure 6.39. NHC/Lewis acid dual‐catalyzed annulation with homoenolates.Figure 6.40. NHC/Lewis acid dual‐catalyzed reactions. (a) NHC/Lewis acid dua...Figure 6.41. A switched reaction pathway enabled by NHC/Lewis acid dual cata...Figure 6.42. Early cooperative catalytic strategies of NHCs and Brønsted aci...Figure 6.43. NHC/Brønsted acid dual‐catalyzed β‐protonation of enals. (a) Sc...Figure 6.44. NHC/thiourea dual‐catalyzed construction of spirocyclic structu...Figure 6.45. Cooperative catalysis of NHCs with other catalysts. (a) Youn’s ...Figure 6.46. Cooperative catalysis of NHCs and HOBt.Figure 6.47. Kinetic resolution of secondary and tertiary alcohols. (a) Suzu...Figure 6.48. Kinetic resolution of alcohols and phenols. (a) Yamada’s NHC‐ca...Figure 6.49. NHC‐catalyzed kinetic resolution of amines.Figure 6.50. NHC‐catalyzed kinetic resolution of imines. (a) Chi’s NHC‐catal...Figure 6.51. NHC‐catalyzed DKR of functionalized ketones. (a) Bode’s NHC‐cat...Figure 6.52. NHC‐catalyzed DKR of esters and pyranones. (a) Chi’s DKR of α,α...Figure 6.53. Acylative desymmetrization of diols. (a) Rovis’s NHC‐catalyzed ...Figure 6.54. Acylative desymmetrization of biphenols. (a) Chi’s NHC‐catalyze...Figure 6.55. Desymmetrization through benzoin and Stetter reactions. (a) Ema...Figure 6.56. Desymmetrization of 1,4‐dienes and 1,3‐diketones. (a) Fang’s NH...Figure 6.57. Total synthesis of (−)‐seragakinone A.Figure 6.58. Formal synthesis of (±)‐platensimycin.Figure 6.59. Total synthesis of roseophilin.Figure 6.60. Total synthesis of Maremycin B.Figure 6.61. Total synthesis of Yohimbine alkaloids.Figure 6.62. Total synthesis of defucogilvocarcins E, M, and V.Figure 6.63. Synthesis of BCDEF ring analogue of fredericamycin A.Figure 6.64. Total synthesis of (−)‐Δ⁹‐tetrahydrocannabinol.Figure 6.65. Total synthesis of (+)‐dactylolide.

7 Chapter 7Scheme 7.1 Chiral organoiodine(III and V) reagents.Scheme 7.2 General catalytic cycles of organoiodine(III/I and V/III) catalys...Scheme 7.3 Challenges in the hypervalent iodine‐mediated enantioselective ox...Scheme 7.4 The first enantioselective dearomatization of 1‐naphthols using c...Scheme 7.5 Kita’s modified spirobiindane‐derived catalyst 20 for highly enan...Scheme 7.6 Design of conformationally flexible first‐generation chiral organ...Scheme 7.7 Lactate‐derived bis‐sec‐amide 25a‐catalyzed highly enantioselecti...Scheme 7.8 Design of 2‐aminoalcohol‐derived organoiodines as conformationall...Scheme 7.9 Conformationally flexible iodoarene 27a‐catalyzed enantioselectiv...Scheme 7.10 Additional methanol effect on the enantioselective dearomatizati...Scheme 7.11 X‐ray structures of extended iodine(I) 27a and folded iodine(III...Scheme 7.12 Enantioselective oxidative cyclization of ortho‐ and para‐hydroq...Scheme 7.13 Enantioselective oxidative spirolactonization of 1‐ and 2‐naphth...Scheme 7.14 Asymmetric total synthesis of (–)‐maldoxin using organoiodine ca...Scheme 7.15 Enantioselective dearomative cyclization using chiral iodoarene ...Scheme 7.16 Enantioselective dearomative C–C coupling.Scheme 7.17 Triazole‐derived C₁‐symmetric iodoarene 33‐catalyzed enantiosele...Scheme 7.18 Structurally unique chiral iodoarene catalysts 34–38.Scheme 7.19 Enantioselective dearomative hydroxylation of 1‐napthol using bi...Scheme 7.20 Examples of natural products synthesized by enantioselective hyd...Scheme 7.21 The first organoiodine‐catalyzed enantioselective para‐dearomati...Scheme 7.22 Lactate‐derived 25c‐catalyzed enantioselective para‐hydroxylatio...Scheme 7.23 Highly enantioselective para‐hydroxylation of phenols using inda...Scheme 7.24 Chiral organoiodine‐catalyzed enantioselective α‐oxytosylation o...Scheme 7.25 Mechanistic consideration of the enantioselective α‐oxytosylatio...Scheme 7.26 Highly enantioselective α‐oxytosylation of enol esters under cat...Scheme 7.27 Highly enantioselective α‐oxytosylation of propiophenone using 3...Scheme 7.28 Bis‐sec‐amide 25c‐catalyzed enantioselective α‐oxyacylation of e...Scheme 7.29 Enantioselective oxylactonization of ketocarboxylic acid.Scheme 7.30 The first chiral organoiodine(III)‐catalyzed enantioselective or...Scheme 7.31 Highly enantioselective α‐fluorination of indanone‐derived β‐ket...Scheme 7.32 Enantioselective α‐fluorination using planar chiral catalyst 63....Scheme 7.33 Enantioselective oxidative Friedel–Crafts type spirocyclizations...Scheme 7.34 Enantioselective cascade oxidative spirocyclization.Scheme 7.35 Enantioselective vicinal dioxygenations of styrene using chiral ...Scheme 7.36 Chiral organoiodine‐catalyzed cascade enantioselective oxidative...Scheme 7.37 Diastereo‐ and enantioselective oxylactonization of ortho‐alkeny...Scheme 7.38 Enantioselective oxidative aminocyclization.Scheme 7.39 Enantioselective oxidative cyclization of unsaturated amides. (a...Scheme 7.40 Organoiodine‐catalyzed enantioselective oxidative fluorocyclizat...Scheme 7.41 Enantioselective fluorocyclization via C–O and C–C bond formatio...Scheme 7.42 Enantioselective vicinal diacetoxylation of styrenes.Scheme 7.43 Catalytic enantioselective vicinal diamination of styrenes.Scheme 7.44 Catalytic enantioselective intermolecular oxyamination of alkene...Scheme 7.45 Catalytic enantioselective vicinal difluorination of alkenes. (a...Scheme 7.46 Catalytic enantioselective geminal difluorination of alkenes. (a...Scheme 7.47 Catalytic enantioselective geminal difluorination of alkenes....Scheme 7.48 Enantioselective oxidative rearrangement of tertiary allylic alc...

8 Chapter 8Scheme 8.1. Enantioselective α‐alkylation of aldehydes: general mechanism.Scheme 8.2. Extension to the enantioselective α‐perfluoroalkylation and β‐cy...Scheme 8.3. Alternative photosensitizers.Scheme 8.4. Enantioselective α‐alkylation of β‐ketocarbonyl compounds and β‐...Scheme 8.5. Enantioselective α‐benzylation of aldehydes with bromo‐derivativ...Scheme 8.6. Enantioselective α‐benzylation of aldehydes with alcohols.Scheme 8.7. Enantioselective α‐alkylation of aldehydes with alkenes.Scheme 8.8. Enantioselective α‐alkynylation of β‐ketocarbonyl compounds.Scheme 8.9. Enantioselective β‐arylation of cyclohexanone.Scheme 8.10. Enantioselective conjugate addition of C‐centered radicals to c...Scheme 8.11. Enantioselective β‐hydroacylation and β‐alkylation of enals.Scheme 8.12. Enantioselective reduction of 1,2‐diketones.Scheme 8.13. Enantioselective reductive dehalogenation of α–α‐dihalogeno aro...Scheme 8.14. Enantioselective photocatalytic synthesis of pyrroloindolines....Scheme 8.15. Enantioselective intramolecular hydroamination of alkenes.Scheme 8.16. Deracemization of cyclic ureas.Scheme 8.17. Enantioselective aza‐pinacol cyclization.Scheme 8.18. Enantioselective Minisci‐type addition reaction of α‐amino acid...Scheme 8.19. Enantioselective Minisci‐type reactions. (a) Isoquinolines as r...Scheme 8.20. Conjugate addition/enantioselective protonation of N‐aryl glyci...Scheme 8.21. Enantioselective conjugate addition of prochiral ketyl radicals...Scheme 8.22. Enantioselective (3+2)‐radical cycloaddition between cyclopropy...Scheme 8.23. Enantioselective reduction of various 2‐azaaryl ketones.Scheme 8.24. Enantioselective syntheses of furoindolines and pyrroloindoline...Scheme 8.25. Conjugate addition/enantioselective protonation of simple alkan...Scheme 8.26. Enantioselective coupling of α‐bromo ketones with N‐aryl α‐amin...Scheme 8.27. Enantioselective coupling of N‐arylaminomethanes with N‐sulfony...Scheme 8.28. Enantioselective coupling of glycine esters derivatives with α‐...Scheme 8.29. Enantioselective photo‐Giese‐type reactions: general mechanism....Scheme 8.30. Examples of enantioselective photo‐Giese‐type reactions. (a) RuScheme 8.31. Various strategies of generation of C‐centered radicals for ena...Scheme 8.32. Enantioselective synthesis of pyrrolo[1,2‐a]indoles.Scheme 8.33. Enantioselective 1,2‐addition reactions of α‐aminoalkyl radical...Scheme 8.34. Enantioselective coupling of α‐silylamines with 2‐acyl imidazol...Scheme 8.35. Enantioselective redox‐neutral coupling of N‐aryl carbamic este...Scheme 8.36. Enantioselective C(sp³)–H functionalization of hydrocarbons wit...Scheme 8.37. Enantioselective reductive coupling of nitrones with aromatic a...Scheme 8.38. Enantioselective (3+2)‐cycloaddition between aryl cyclopropyl k...Scheme 8.39. Enantioselective α‐functionalization of 2‐acyl imidazoles.Scheme 8.40. Enantioselective α‐hydroxylation of cyclic β‐ketoesters.Scheme 8.41. Bifunctional photoamino‐catalyzed enantioselective alkylation o...Scheme 8.42. Chiral acridinium salt‐catalyzed enantioselective anti‐Markovni...Scheme 8.43. Chiral oxopyrylium salt‐catalyzed enantioselective Diels–Alder ...Scheme 8.44. Urea as redox‐active directing group for enantioselective (3+2)...Scheme 8.45 Chiral Brønsted acid‐photocatalyzed enantioselective reactions. ...Scheme 8.46. Chiral phosphoric acid‐photocatalyzed enantioselective reaction...Scheme 8.47. Chiral iridium‐catalyzed photoinduced enantioselective alkylati...Scheme 8.48. Chiral iridium‐catalyzed photoinduced enantioselective alkylati...Scheme 8.49. Chiral iridium‐catalyzed α‐functionalization of acyl imidazole ...Scheme 8.50. Rhodium photocatalyzed enantioselective amination.Scheme 8.51 Enantioselective β‐alkylation of α,β‐unsaturated 2‐acyl imidazol...Scheme 8.52. Enantioselective photocatalytic [3+2]‐cycloaddition.Scheme 8.53. Asymmetric copper‐catalyzed C–N cross‐couplings.Scheme 8.54. Copper‐catalyzed enantioselective alkylation of N‐cyclic sulfon...Scheme 8.55 Nickel‐catalyzed enantioselective reactions between α,β‐unsatura...Scheme 8.56 Copper‐catalyzed enantioselective difunctionalization of styrene...Scheme 8.57. Copper‐catalyzed enantioselective cyanoalkylation of styrenes....

9 Chapter 9Figure 9.1 Enhancing the potential of generic modes of catalytic reactivity ...Figure 9.2 The two photochemical mechanisms available to promote asymmetric ...Scheme 9.1 Enantioselective catalytic α‐alkylation of aldehydes enabled by i...Scheme 9.2 Enantioselective α‐alkylation of cyclic ketones via photochemical...Scheme 9.3 Phase‐transfer‐catalyzed enantioselective perfluoroalkylation of ...Scheme 9.4 Enantioselective catalytic radical conjugate addition driven by t...Scheme 9.5 (a) Direct excitation of chiral enamines in the enantioselective ...Scheme 9.6 The direct photoexcitation of catalytic chiral iminium ions XIX e...Scheme 9.7 Enantioselective photochemical organocatalytic β‐alkylation of en...Scheme 9.8 Enantioselective photocatalytic C‐H functionalization of toluene ...Figure 9.3 The two enantioisomers of octahedral chiral‐at‐metal catalysts.Scheme 9.9 Photochemical asymmetric α‐alkylation of acyl imidazoles enabled ...Scheme 9.10 Photochemical asymmetric β‐C−H functionalization of 2‐acyl azaar...Scheme 9.11 Stereoselective synthesis of 1,2‐amino alcohols with visible‐lig...Scheme 9.12 Asymmetric conjugate addition of α‐amino radicals to α,β‐unsatur...Scheme 9.13 Asymmetric copper‐catalyzed C‐N cross‐couplings induced by visib...Scheme 9.14 Photoexcitation of the (η³‐allyl)iridium(III) complex XLIII prom...Scheme 9.15 Photoexcitation of a NAD(P)H‐dependent enzyme enables a non‐natu...Scheme 9.16 Photoenzymatic radical cyclization: Flavin hydroquinone cofactor...Scheme 9.17 Photoenzymatic enantioselective intermolecular radical coupling....Scheme 9.18 Photoexcitation of flavin‐dependent “ene”‐reductases promotes th...Scheme 9.19 Asymmetric β‐allylation and β‐sulfonylation of α,β‐unsubstituted...Scheme 9.20 Enantioselective acyl radical addition to enals to afford 1,4‐di...Scheme 9.21 Visible‐light‐driven asymmetric nickel‐catalyzed acyl cross‐coup...

10 Chapter 10Figure 10.1. Stoichiometric amounts of template (−)‐ent−1 can bind to quinol...Figure 10.2. Catalyst (+)‐4 transfers triplet energy preferentially to the b...Figure 10.3. E and Z alkenes afford almost the same d.r. of cyclobutane prod...Figure 10.4. The first intermolecular catalytic enantioselective [2+2] photo...Figure 10.5. Thioxanthone catalyst (+)−13 absorbs visible light and can be u...Figure 10.6. Catalyst (+)−13 sensitizes the enantioselective intermolecular ...Figure 10.7. Thiourea 18 binds to coumarins 19 and catalyzes their intramole...Figure 10.8. Chiral phosphoric acid 21 binds to β‐carboxyl‐substituted cycli...Figure 10.9. Chiral diamine 24 generates an intermediate charge‐transfer com...Figure 10.10. Iridium catalyst 29 catalyzes the enantioselective [2+2] photo...Figure 10.11. Iridium catalyst 32 catalyzes the intermolecular enantioselect...Figure 10.12. Rhodium complex 35 catalyzes the enantioselective [2+2] photoc...Figure 10.13. A terbium(III) catalyst with chiral N,N‐dioxide ligand 38 cata...Figure 10.14. AlBr₃‐activated oxazaborolidine catalysts 41, 42, and 43 were ...Figure 10.15. A variety of coumarins 44 underwent successful [2+2] photocycl...Figure 10.16. AlBr₃‐activated oxazaborolidine catalysts 41, 42, and 43 were ...Figure 10.17. The enantioselective intermolecular [2+2] photocycloaddition o...Figure 10.18. Coordination of a Lewis acid to enones induces changes in the ...Figure 10.19. Upon coordination to a Lewis acid, there is a marked bathochro...Figure 10.20. The enantioselective [2+2] photocycloaddition of acyclic enone...Figure 10.21. The enantioselective [2+2] photocycloaddition of 2′‐hydroxycha...Figure 10.22. The enantioselective [2+2] photocycloaddition of 2′‐hydroxycha...Figure 10.23. The enantioselective [2+2] photocycloaddition of cinnamates 58Figure 10.24. Formation of an eniminium ion induces changes in the excited‐s...Figure 10.25. The eniminium ion 61 of cinnamic aldehyde, formed with catalyt...Figure 10.26. N,O‐acetals 63 exist as a mixture of open and closed forms (63...Figure 10.27. N,O‐acetals 63 react enantioselectively with alkenes 66 in the...Figure 10.28. The enantioselective [2+2] photocycloaddition of 1‐bromoacenap...

11 Chapter 11Scheme 11.1. Palladium‐catalyzed arylation of vinyl triflates 1.Scheme 11.2. Palladium‐catalyzed asymmetric synthesis of dibenzazepinones 6....Scheme 11.3. Palladium‐catalyzed desymmetrization toward 3,4‐dihydroisoquino...Scheme 11.4. Palladium‐catalyzed atroposelective olefination of arene 11....Scheme 11.5. Palladium‐catalyzed atroposelective C−H arylation toward hetero...Scheme 11.6. Palladium‐catalyzed desymmetrization of 2‐(arylsilyl)aryl trifl...Scheme 11.7. Palladium‐catalyzed desymmetrization using MPAA 23.Scheme 11.8. Palladium‐catalyzed olefination of α,α‐diphenylacetat...Scheme 11.9. Palladium‐catalyzed C–H iodination of diarylmethylamines 29....Scheme 11.10. Palladium‐catalyzed asymmetric functionalization of ferrocenes...Scheme 11.11. Palladium‐catalyzed enantioselective functionalization of aren...Scheme 11.12. Enantioselective C–H activation using phosphordiamidite ligand...Scheme 11.13. Enantioselective C–H activation using sulfoxide‐oxazoline liga...Scheme 11.14. Palladium‐catalyzed atroposelective transformations of biaryls...Scheme 11.15. Palladium‐catalyzed atroposelective olefination of arenes 68....Scheme 11.16. Palladium‐catalyzed diastereoselective C–H activation of biary...Scheme 11.17. Palladium/chiral norbornene cooperative catalysis.Scheme 11.18. Atroposelective pallada‐electrocatalyzed C−H activation.Scheme 11.19. Rhodium‐catalyzed enantioselective C–H annulation.Scheme 11.20. Rhodium‐catalyzed enantioselective C–H allylation.Scheme 11.21. Rhodium‐catalyzed enantioselective synthesis of isoindolones....Scheme 11.22. Rhodium‐catalyzed spiroannulation toward dearomatized naphthol...Scheme 11.23. Rhodium‐catalyzed axial‐to‐central chirality transfer toward s...Scheme 11.24. Rhodium‐catalyzed C–H activation toward cyclopentenylamines....Scheme 11.25. Rhodium‐catalyzed enantioselective dual C–H activation.Scheme 11.26. Rhodium‐catalyzed enantioselective addition of nitroalkenes 11...Scheme 11.27. Rhodium‐catalyzed enantioselective three‐component coupling....Scheme 11.28. Rhodium‐catalyzed atroposelective C–H allylation.Scheme 11.29. Rhodium‐catalyzed atroposelective synthesis of C–N axially chi...Scheme 11.30. Rhodium‐catalyzed C–H activation using hybrid catalysts.Scheme 11.31. Rhodium‐catalyzed hydroarylation of ketimine 129.Scheme 11.32. Rhodium‐catalyzed synthesis of spirosilabifluorone derivatives...Scheme 11.33. Rhodium‐catalyzed C–H activation using chiral carboxylic acid Scheme 11.34. Rhodium‐catalyzed C–H arylation of ferrocenes 140.Scheme 11.35. Rhodium‐catalyzed C–H activation with artificial metalloenzyme...Scheme 11.36. Early example of the enantioselective hydroarylation of norbor...Scheme 11.37. Enantioselective hydroheteroarylation of bicycloalkanes 145....Scheme 11.38. Enantioselective hydroarylations of norbornenes 145.Scheme 11.39. Enantioselective C−H alkylation of indole derivatives 158.Scheme 11.40. Enantioselective hydroarylation of anilides 160 and thiophene Scheme 11.41. Enantioselective C−H addition to α‐ketoamides 165.Scheme 11.42. Enantioselective C−H alkylation of ferrocenes 168.Scheme 11.43. Enantioselective C−H borylation with the aid of (a) silyl and ...Scheme 11.44. Enantioselective remote C−H borylation of (a) benzhydrylamides...Scheme 11.45. Iridium‐catalyzed enantioselective C−H silylation.Scheme 11.46. Ruthenium(II)‐catalyzed intramolecular C–H alkylation of (a) n...Scheme 11.47. Enantioselective ruthenium(II)‐catalyzed C–H alkylation by chi...Scheme 11.48. Scandium‐catalyzed enantioselective C–H activations: (a) inter...Scheme 11.49. Enantioselective nickel‐catalyzed hydrocarbamoylations of alke...Scheme 11.50. Nickel‐catalyzed asymmetric alkylation of pyridones: (a) early...Scheme 11.51. Nickel‐catalyzed exo‐selective hydroarylation.Scheme 11.52. Enantioselective nickel‐catalyzed hydroarylation under aluminu...Scheme 11.53. Nickel‐catalyzed enantioselective intramolecular C–H activatio...Scheme 11.54. Enantioselective nickel(0)‐catalyzed reductive three‐component...Scheme 11.55. Enantioselective cobalt‐catalyzed intramolecular hydroacylatio...Scheme 11.56. Enantioselective cobalt‐catalyzed hydroarylation of styrenes 1...Scheme 11.57. Enantioselective cobalt(III)‐catalyzed alkylation of indoles 2...Scheme 11.58. Enantioselective amidation of (a) thioamides 252 and (b) ferro...Scheme 11.59. Chiral cyclopentadienyl cobalt(III)‐catalyzed C–H functionaliz...Scheme 11.60. Copper‐catalyzed enantioselective allylation.Scheme 11.61. Early example on enantioselective iron‐catalyzed C–H activatio...Scheme 11.62. Enantioselective iron‐catalyzed C–H secondary alkylation.

12 Chapter 12Scheme 12.1. Various modes of C(sp³)–H activation.Scheme 12.2. C(sp³)–H bond insertion by metal carbenoids and metal nitrenoid...Scheme 12.3. General catalytic cycle of C(sp³)–H bond insertion by metal car...Figure 12.1. Classification of metal carbenoids.Scheme 12.4. C–H insertion of alkanes with aryldiazoacetates. (a) C–H insert...Scheme 12.5. C–H insertion of alkanes with azavinyl carbenoids.Scheme 12.6. C–H insertion of primary and secondary C–H bonds with Rh porphy...Scheme 12.7. Highly selective C–H insertion of primary C–H bonds.Scheme 12.8. Highly selective carbenoid insertion into secondary C–H bonds....Scheme 12.9. Highly selective carbenoid insertion into tertiary C–H bonds....Figure 12.2. Chiral metal complexes for asymmetric C–H insertion of 1,4‐cycl...Scheme 12.10. C–H insertion of electron‐deficient methyl sites.Scheme 12.11. C–H insertion of allylic and benzylic C–H bonds with triazoles...Scheme 12.12. Synthesis of β‐arylpyrrolidines.Scheme 12.13. Carbenoid insertion into benzylic C–H bonds of substituted eth...Scheme 12.14. Carbenoid insertion into benzylic C–H bonds of benzyl silyl et...Scheme 12.15. Synthesis of 2,3‐dihydrobenzofurans by sequential C–H function...Scheme 12.16. Synthesis of 2,3‐dihydrobenzofurans by sequential C–H function...Figure 12.3. Immobilized Cu(box) complex.Scheme 12.17. C–H insertion of phthalan and dihydrofuran derivatives.Scheme 12.18. C–H insertion of silicon‐substituted alkanes with 1‐sulfonyl‐1...Scheme 12.19. C–H insertion of silicon‐substituted alkanes with aryl diazoac...Scheme 12.20. Application of the combined C–H functionalization/Cope rearran...Scheme 12.21. Intramolecular C–H insertion with α‐diazosulfones. (a) Synthes...Figure 12.4. Chiral metal catalysts used for synthesis of β‐lactones.Scheme 12.22. Intramolecular C–H insertion by non‐diazo approaches. (a) Synt...Scheme 12.23. C–H insertion in carbene/alkyne metathesis (CAM).Scheme 12.24. General catalytic cycle of C(sp³)–H bond insertion of metal ni...Figure 12.5. Chiral metal catalysts used for C–H amination of indane.Scheme 12.25. Diastereoselective C–H amination of indane with chiral sulfoni...Scheme 12.26. Enantioselective intermolecular benzylic C–H amination with su...Scheme 12.27. Enantioselective intermolecular benzylic C–H amination with su...Figure 12.6. Chiral metal catalysts used for the synthesis of cyclic sulfami...Scheme 12.28. Enantioselective intermolecular benzylic C–H amination with su...Figure 12.7. Chiral metal catalysts used for C–H amination with azides.Scheme 12.29. Diastereoselective C–H amination of indane with chiral sulfoni...Figure 12.8. Chiral metal catalysts used for C–H amination with dioxazolones...Scheme 12.30. Asymmetric synthesis of γ‐lactams via C–H amidation enabled by...Scheme 12.31. Asymmetric enzymatic C–H primary amination.Scheme 12.32. Concerted metalation‐deprotonation (CMD).Scheme 12.33. Early discovery of C(sp³)–H activation.Scheme 12.34. Dyker’s synthesis of benzocyclobutane.Scheme 12.35. Pd(0)/PAr₃‐catalyzed intramolecular arylation.Scheme 12.36. Pd(0)‐catalyzed enantioselective intramolecular arylation.Scheme 12.37. Baudoin’s asymmetric synthesis of indanes.Scheme 12.38. Pd(0)‐catalyzed arylation of unactivated acylic methylenes.Scheme 12.39. Chiral phosphoric acid catalyst promoted intramolecular arylat...Scheme 12.40. Enantioselective intramolecular arylation of cyclopropanes.Scheme 12.41. Enantioselective trifluoroacetimidoylation of cyclopropane.Scheme 12.42. Pd(0)‐catalyzed directed intermolecular arylation.Scheme 12.43. Cramer’s synthesis of chiral β‐lactams.Scheme 12.44. Cramer’s synthesis of chiral γ‐lactams.Scheme 12.45. Pd(II) catalysis for C(sp³)–H activation.Scheme 12.46. Yu’s preliminary asymmetric C(sp³)–H activation.Scheme 12.47. Oxidative arylation of α‐tertiary amide.Scheme 12.48. Oxidative arylation with aryl boronic acid.Scheme 12.49. Enantioselective desymmetrization of thioamide.Scheme 12.50. Enantioselective desymmetrization of triflamide.Scheme 12.51. Arylation of cyclic α‐tertiary carboxylic acids.Scheme 12.52. Arylation of aliphatic amines. (a) β‐C(sp³)–H amination. (b) β...Scheme 12.53. Redox‐neutral arylation of C(sp³)–H bond in small rings.Scheme 12.54. Directed arylation of benzylic positions.Scheme 12.55. Arylation of aldehyde/ketone via transient directing group str...Scheme 12.56. (Top and bottom) Bidentate‐ligand‐enabled arylation of unactiv...Scheme 12.57. Phosphoric acid enabled arylation of unactivated methylenes.Scheme 12.58. Arylation of cyclopropane‐containing acids/amines.Scheme 12.59. Directed enantioselective borylation of cyclobutane.Scheme 12.60. Enantioselective fluorination of benzylic position.Scheme 12.61. Synthesis of chiral aziridines.Scheme 12.62. Synthesis of chiral β‐lactams.Scheme 12.63. Benzoquinone‐assisted Pd(0)‐catalyzed allylic C(sp³)–H activat...Scheme 12.64. Enantioselective allylic C(sp³)–H alkylation.Scheme 12.65. Enantioselective allylic C(sp³)–H acetoxylation.Scheme 12.66. Asymmetric intramolecular oxidation of allylic C(sp³)–H bond....Scheme 12.67. Chiral‐Ir(III) catalyzed amination of methyl group.Scheme 12.68. Co(III) and Rh(III)‐catalyzed asymmetric amination reactions....Scheme 12.69. Ir(III) and Rh(III)‐catalyzed asymmetric C(sp³)–H activation....Scheme 12.70. General mechanism of C–H activation via oxidative addition.Scheme 12.71. Achiral allylic C–H activation/C–C bond formation by Yu.Scheme 12.72. Asymmetric allylic C–H activation/C–C bond formation by Yu.Scheme 12.73. Enantioselective alkylation of allyl benzene by Mita and Sato....Scheme 12.74. α‐Nitrogen C(sp³)–H alkylation of linear amines by Shibata....Scheme 12.75. α‐Nitrogen C(sp³)–H alkylation of cyclic amines by Shibata.Scheme 12.76. Two‐fold C(sp³)–H alkylation of N‐methyl amines by Nishimura....Scheme 12.77. C(sp³)–H alkylation of methyl amines and ethers by Ohmura and ...Scheme 12.78. Tandem dehydrogenation/C–H alkylation by Suginome.Scheme 12.79. Modification of C(sp³)–H borylation mechanisms based on used l...Scheme 12.80. C(sp³)–H borylation directed by pyridine by Sawamura.Scheme 12.81. Carbonyl directed C(sp³)–H borylation by Sawamura.Scheme 12.82. Carbonyl directed C(sp³)–H γ‐borylation by Sawamura.Scheme 12.83. C(sp³)–H borylation of cyclopropanes by Xu.Scheme 12.84. C(sp³)–H borylation of cyclobutanes by Xu.Scheme 12.85. Pyrazole‐directed C(sp³)–H borylation by Xu.Scheme 12.86. C(sp³)–H borylation of tetrahydroisoquinolines and other azahe...Scheme 12.87. Carbonyl directed C(sp³)–H borylation by Xu.Scheme 12.88. The proposed catalytic cycles for transition metal‐catalyzed C...Scheme 12.89. Achiral C(sp³)–H dehydrogenative silylations.Scheme 12.90. First enantioselective C(sp³)–H dehydrogenative silylations.Scheme 12.91. Enantioselective C(sp³)–H silylation of cyclopropanes by Hartw...Scheme 12.92. The two‐step protocol for C(sp³)–H silylation by Hartwig.Scheme 12.93. Enantioselective C(sp³)–H silylation by He.Scheme 12.94. Ir‐catalyzed C(sp³)–H activation/silylation by Hartwig.Scheme 12.95. Ir‐catalyzed C(sp³)–H activation/silylation of amines by Hartw...

13 Chapter 13Scheme 13.1. Pd‐catalyzed asymmetric synthesis of allylic fluorides.Scheme 13.2. Pd‐catalyzed enantioselective fluorination of acyclic allylic c...Scheme 13.3. Ir‐catalyzed enantioselective fluorination of allylic trichloro...Scheme 13.4. Pd‐catalyzed oxidative 1,2‐fluoroarylation of styrenes.Scheme 13.5. 1,1‐Fluoarylation of allyl amines.Scheme 13.6. Heck arylation‐oxidative fluorination.Scheme 13.7. Catalytic enantioselective fluorination of β‐ and α‐ketoesters....Scheme 13.8. Pd‐catalyzed enantioselective α‐arylation of α‐fluoroketones.Scheme 13.9. S_N2 reactivity of the Colby pro‐enolates with MBH carbonates....Scheme 13.10. Mannich reactions of 2‐fluoro‐1,3‐diketones/hydrates and isati...Scheme 13.11. 1,3‐Dipolar cycloaddition of azomethine ylides with β‐fluoroac...Scheme 13.12. S_N2 fluorination of alkyl bromides by copper(I) fluoride compl...Scheme 13.13. Enantioselective fluorination of α‐aryl cyclohexanones.Scheme 13.14. α‐Fluorination of β‐ketoesters.Scheme 13.15. Asymmetric fluorocyclization of allylic amines.Scheme 13.16. Electrophilic fluorination of allylic alcohol substrates.Scheme 13.17. Fluorocyclization of tryptamines.Scheme 13.18. Asymmetric β‐fluoroamine synthesis from β‐haloamines.Scheme 13.19. Asymmetric α‐fluorination of aldehydes.Scheme 13.20. Asymmetric α‐fluorination of α‐substituted aldehydes.Scheme 13.21. Selective α‐fluorination of ketones.Scheme 13.22. Asymmetric fluorination of 1,3‐dicarbonyl compounds.Scheme 13.23. NHC‐catalyzed oxidative α‐fluorination of aldehydes.Scheme 13.24. Fluorination of 2‐substituted (E)‐cinnamamides.Scheme 13.25. Preparation of chiral α‐chloroaldehydes from enals.Scheme 13.26. Three‐step synthesis of chiral α‐chloroketones from enaminones...Scheme 13.27. Asymmetric vicinal dichlorination of styrenes, allylic alcohol...Scheme 13.28. Asymmetric chlorocyclization reactions.Scheme 13.29. Desymmetrizing chlorination of diolefins using chiral sulfide ...Scheme 13.30. Kinetic resolution of allylic amides through an intramolecular...Scheme 13.31. Asymmetric chlorination of α‐substituted β‐ketoesters.Scheme 13.32. Asymmetric chloroetherification of enones catalyzed by chiral Scheme 13.33. Asymmetric chloroamination of unsaturated olefins catalyzed by...Scheme 13.34. Kinetic resolution of tetrahydropyridine allyl chlorides.Scheme 13.35. Asymmetric bromoamination of chalcones with NBS catalyzed by c...Scheme 13.36. Asymmetric haloazidation of allylic alcohols.Scheme 13.37. Asymmetric haloazidation of allylic alcohols.Scheme 13.38. Enantioselective bromoaminocyclization of tosylcarbamate deriv...Scheme 13.39. Asymmetric organocatalytic bromolactonization of α‐exo‐methyle...Scheme 13.40. Asymmetric organocatalytic bromohydroxylation of aryl olefins ...Scheme 13.41. Asymmetric organocatalytic 5‐exo and 6‐endo‐bromolactonization...Figure 13.1. BINAP ligands used in bromofunctionalization reactions.Scheme 13.42. Enantioselective bromolactonization of deactivated olefinic ac...Scheme 13.43. Organocatalysts used in the asymmetric α‐bromination of aldehy...Scheme 13.44. Mechanism of cyclization by iodoamination or iodolactonization...Scheme 13.45. Asymmetric iodoamination reaction developed by Jacobsen’s grou...Scheme 13.46. Iodoaminocyclization procedure developed by Tripathi and Mukhe...Scheme 13.47. Effects of KBr vs KI additive in the iodoaminocyclization reac...Scheme 13.48. TRIP‐catalyzed enantioselective addition of NIS to enecarbamat...Scheme 13.49. Formation of chiral cyclic ureas described by Struble and cowo...Scheme 13.50. Iodoamination with concomitant trapping of CO₂.Scheme 13.51. Enantioselective iodolactonizations catalyzed by tri‐Zn comple...Scheme 13.52. Desymmetrization of diallylacetic acid derivatives catalyzed b...Scheme 13.53. Desymmetrization reaction described by the Johnston group.

14 Chapter 14Scheme 14.1. Enzymatic kinetic resolution (R isomer is considered the fast‐r...Scheme 14.2. Enzymatic repeated kinetic resolution.Scheme 14.3. Parallel kinetic resolution (PKR).Scheme 14.4. Dynamic kinetic resolution (DKR) general scheme.Scheme 14.5. Deracemization procedures for obtaining optically active compou...Scheme 14.6. Desymmetrization of prochiral or meso‐compounds.Scheme 14.7. Schematic stereopreference of lipases.Scheme 14.8. Examples of hydrolytic KRs catalyzed by lipases. (a) Stereosele...Scheme 14.9. Some examples of lipase‐catalyzed KRs via O‐ and N‐acylations. ...Scheme 14.10. KRs via oxygen insertion in C–H bonds employing oxidoreductase...Scheme 14.11. DKRs employing metal catalysts for the substrate racemization....Scheme 14.12. Biocatalyzed DKRs employing transaminases and alcalases. (a) D...Scheme 14.13. Some examples of DYRKR for the synthesis of optically active c...Scheme 14.14. Some examples of deracemizations catalyzed by enzymes for the ...Scheme 14.15. Parallel kinetic resolutions catalyzed by oxidative biocatalys...Scheme 14.16. Desymmetrization of prochiral compounds catalyzed by different...Scheme 14.17. Synthesis of valuable compounds in enzymatic desymmetrizations...Scheme 14.18. Transaminase‐catalyzed desymmetrization procedures. (a) Synthe...Scheme 14.19. Multienzymatic systems for the preparation of valuable chiral ...Scheme 14.20. Multicatalytic systems combining enzymes and organocatalysts f...

15 Chapter 15Scheme 15.1. Rhodium‐catalyzed AH of functionalized alkenes with the general...Figure 15.1. Rhodium‐catalyzed AH of some less common substrates.Scheme 15.2. AH of cyclic α‐dehydro ketones and synthesis of β,β‐diaryl‐α‐am...Scheme 15.3. AH of α‐formyl and conjugated enamides.Scheme 15.4. Hydrogenation of itaconic acid analogues.Figure 15.2. Rhodium‐catalyzed AH of less conventional enamides.Scheme 15.5. AH of other enamides: conjugated, β‐aryl bicyclic, and tetrasub...Scheme 15.6. AH of enol ester derivatives: 1‐alkyl vinyl esters and aryl vin...Scheme 15.7. Preparation of 1,2‐difunctional products by rhodium‐catalyzed A...Scheme 15.8. AH involving supramolecular interactions between the catalyst a...Scheme 15.9. Hydrogenative desymmetrization reactions and kinetic resolution...Scheme 15.10. Rhodium‐catalyzed AH of α‐ or β‐trifluoromethyl‐substituted ac...Scheme 15.11. Preparation of acyclic and cyclic sulfones by rhodium‐catalyze...Scheme 15.12. Cobalt‐catalyzed AH of α‐N‐acyl acrylates and enamides with ne...Scheme 15.13. AH of α‐N‐acyl acrylates and enamides with cationic cobalt(I) ...Scheme 15.14. Nickel‐catalyzed AH of α,β‐unsaturated esters and α‐N‐acyl acr...Scheme 15.15. AH of alkenes without any specific requirement in terms of the...Scheme 15.16. Iridium‐catalyzed AH of α,β‐unsaturated acid derivatives: male...Scheme 15.17. Iridium‐catalyzed AH of exocyclic compounds.Scheme 15.18. Iridium‐catalyzed AH of (poly)cyclic compounds.Scheme 15.19. Iridium‐catalyzed hydrogenation and spiroketalization of bis(2...Scheme 15.20. AH of alkenylboronic esters and chloro alkenyl boronic esters....Scheme 15.21. Iridium‐catalyzed AH of sulfones and fluorine‐substituted olef...Scheme 15.22. Ruthenium‐catalyzed AH of isocoumarines and benzothiophene dio...Scheme 15.23. Asymmetric hydrogenation of (E)‐2‐methyl‐2‐stilbene (S72) usin...Figure 15.3. Chiral P,N‐ligands bearing heterocycles other than oxazolines u...Figure 15.4. Chiral phosphinoamines and phosphinites as P,N‐ligands used in ...Figure 15.5. Phosphinoferrocenyl ligands and a P‐stereogenic pyridyl‐dihydro...Figure 15.6. Phosphites as phosphorus donors in P,N‐ligands for the iridium‐...Figure 15.7. Chiral P,O‐ and P,S‐ligands used in the iridium‐catalyzed asymm...Figure 15.8. Chiral C,N‐ligands with N‐heterocyclic carbenes reported for th...Scheme 15.24. Hydrogenation of trisubstituted unfunctionalized alkenes and d...Scheme 15.25. Examples of asymmetric hydrogenation of 1,1‐disubstituted alke...Scheme 15.26. Examples of asymmetric hydrogenation of tetrasubstituted olefi...Scheme 15.27. Rh‐catalyzed hydrogenation of unfunctionalized olefins.Scheme 15.28. Co‐catalyzed hydrogenation of unfunctionalized olefins.Scheme 15.29. Synthesis of an intermediate (P93) of hepaindole alkaloids by ...Scheme 15.30. Selected examples of AH of bicyclic ketones by Boehringer‐Inge...Scheme 15.31. Selected examples of AH by Ohkuma’s rutenabicyclic catalysts C...Scheme 15.32. Initial (η⁶‐Arene)/N‐Ts‐diamine ruthenium catalysts (C16). Sel...Figure 15.9. Mohar’s catalyst for ATH.Figure 15.10. Other ruthenium catalysts: bimetallic, cyclometallated, and wi...Figure 15.11. Chiral η⁵ C₅Me₅ (Cp*)‐rhodium and iridium complexes.Scheme 15.33. Rhodium‐catalyzed AHs of ketones with P‐stereogenic bisphosphi...Scheme 15.34. Rhodium‐catalyzed AH of 2‐pyridine ketones.Scheme 15.35. Rhodium‐catalyzed AH of aryl perfluoroalkyl ketones and triflu...Scheme 15.36. Selected examples of AH of alkyl aryl ketones by the iridium c...Scheme 15.37. AH of aryl ketones by iridium‐SpiroPAP complexes.Scheme 15.38. AH of alkyl ketones by iridium‐SpiroPNP complexes.Scheme 15.39. Selected examples of the AH of simple ketones by iridium compl...Scheme 15.40. Iridium‐catalyzed AH of diaryl ketones.Figure 15.12. Structures of Iridium complexes with chiral NHC employed in th...Figure 15.13. Open‐chain N₂P₂‐ligand and macrocyclic ligands used in the pre...Figure 15.14. Iron catalysts for the ATH or AH of ketones.Scheme 15.41. AH of aromatic ketones using iron complex C45.Figure 15.15. Initial manganese complexes for AH and ATH.Scheme 15.42. AH catalyzed by a manganese complex.Scheme 15.43. Selected examples of asymmetric hydrogenation of isoquinolines...Scheme 15.44. Hydrogenation of pyrimidines and benzoxazinones with Ir‐P,P ca...Scheme 15.45. Hydrogenation of 1‐pyrrolines and pyridinium salts with Ir‐P,NScheme 15.46. AH of various N‐aromatic heterocycles with ruthenium arene‐dia...Scheme 15.47. Ruthenium‐catalyzed AH of quinoxalines with an NHC ligand.Scheme 15.48. Biomimetic asymmetric hydrogenation of benzoxazinones.Scheme 15.49. Cobalt‐ and nickel‐catalyzed AH of sulfonyl ketimines and benz...Scheme 15.50. Iron‐catalyzed ATH and AH of phosphinyl imines.Scheme 15.51. Cooperative iron‐catalyzed asymmetric hydrogenation of N‐pheny...Scheme 15.52. Asymmetric hydrogenation of N‐aryl and N‐alkyl imines.Scheme 15.53. Asymmetric hydrogenation of O‐alkyl oximes.Scheme 15.54. Intramolecular asymmetric reductive amination (ARA).Scheme 15.55. Intermolecular asymmetric reductive amination (ARA).

16 Chapter 16Figure 16.1. Selection of bioactive and pharmaceutically active compounds co...Scheme 16.1. Enantioselective addition of Grignard reagents to aldehydes cat...Scheme 16.2. Cu(I)‐catalyzed enantioselective addition of Grignard reagent t...Scheme 16.3. Arylation of ketones catalyzed by Ti/Binol (a) [21] and Mg/Bino...Scheme 16.4. Rh(I)‐catalyzed enantioselective addition of arylboroxines to k...Scheme 16.5. Rh‐catalyzed enantioselective arylation of keto esters (a) [31]...Scheme 16.6. Ni‐catalyzed enantioselective arylation of ketones with organob...Scheme 16.7. Cu(I)‐catalyzed enantioselective intramolecular addition of ary...Scheme 16.8. Catalytic enantio‐ and diastereoselective synthesis of adjacent...Scheme 16.9. Addition of allyl and allenyl organoboron reagents to ketones, ...Scheme 16.10. Enantioselective allylation of ketones containing a tri‐, a di...Scheme 16.11. Enantioselective allylboration of ketones catalyzed by 1,16‐di...Scheme 16.12. Zn(II)‐catalyzed enantioselective allenylation of ketones [44]...Scheme 16.13. Catalytic enantioselective propargylation of trifluoromethyl k...Scheme 16.14. Catalytic enantioselective propargylation of aryl ketones [47]...Scheme 16.15. Catalytic enantioselective arylation of ketones with organotit...Figure 16.2. Selection of bioactive and pharmaceutically active compounds co...Scheme 16.16. Cu(I)‐catalyzed enantioselective alkylation of silyl/aryl (a) ...Scheme 16.17. Rh(I)‐catalyzed enantioselective arylation of acyclic (a) [62]...Scheme 16.18. Rh(I)‐catalyzed enantioselective additions of arylboronic acid...Scheme 16.19. Rh(I)‐catalyzed enantioselective arylation of isatin‐derived N...Scheme 16.20. Pd(II)‐catalyzed enantioselective arylation of cyclic α‐ketimi...Scheme 16.21. Pd(II)‐catalyzed enantioselective arylation cyclic ketimines [...Scheme 16.22. Pd(II)‐catalyzed enantioselective arylation of trifluoromethyl...Scheme 16.23. Pd(II)‐catalyzed enantioselective arylation of isatin‐derived ...Scheme 16.24. Pd(II)‐catalyzed enantioselective arylation of cyclic seven‐me...Scheme 16.25. Ni(II)‐catalyzed enantioselective arylations (a) [94] and alke...Scheme 16.26. Co‐catalyzed enantioselective allylation of cyclic ketimines [...Scheme 16.27. Cu(I)‐catalyzed diastereoselective and enantioselective additi...Scheme 16.28. Catalytic Cu(I)‐catalyzed synthesis of C‐tertiary amine from u...Scheme 16.29. Alkenyl‐substituted N‐heteroaromatics as Michael acceptors in ...Scheme 16.30. Lewis acid enabled Cu(I)‐catalyzed conjugate additions to unac...Scheme 16.31. Cu(I)‐catalyzed enantioselective addition of Grignard reagents...Scheme 16.32. Cu(I)‐catalyzed enantioselective addition of Grignard reagents...Scheme 16.33. Cu(I)‐catalyzed enantioselective addition of Grignard reagents...Scheme 16.34. Cu(I)‐catalyzed enantioselective reactions with N‐heteroaromat...Scheme 16.35. Catalytic enantioselective conjugate additions of organozinc r...Scheme 16.36. Selection of successful chiral ligands developed for catalytic...Scheme 16.37. Cu(I)‐catalyzed conjugate additions of organozinc reagents to ...Scheme 16.38. Cu(I)‐catalyzed conjugate additions of organozinc reagents to ...Scheme 16.39. Selection of successful chiral ligands developed for catalytic...Scheme 16.40. Selection of successful chiral ligands developed for catalytic...Scheme 16.41. Cu(I)‐catalyzed conjugate additions of organozirconium reagent...Scheme 16.42. Cu(I)‐catalyzed conjugate additions of organozirconium reagent...Scheme 16.43. Rh(I)‐catalyzed conjugate additions of organoboron reagents to...Scheme 16.44. Rh(I)‐catalyzed conjugate additions of boronic acids to α,β‐un...Scheme 16.45. Rh(I)‐catalyzed conjugate addition of boronic acids to cyclic ...Scheme 16.46. Rh(I)‐catalyzed conjugate addition of organoboron reagent to a...Scheme 16.47. Copper(I)‐catalyzed conjugate addition of arylboron reagents t...Scheme 16.48. Rh(I)‐catalyzed conjugate addition of arylboronic acids to var...Scheme 16.49. Rh(I)‐catalyzed enantioselective synthesis of 3,3‐diaryl‐SPINO...Scheme 16.50. Selection of successful chiral ligands developed for catalytic...Scheme 16.51. Rh(I)‐catalyzed enantioselective synthesis of chiral indole (a...Scheme 16.52. Cu(I)‐carbene catalyzed conjugate additions to α,β‐unsaturated...Scheme 16.53. Rh(I)‐catalyzed enantioselective arylation of sulfolene (a) [2...Scheme 16.54. Rh(I)‐catalyzed enantioselective arylation of α,β‐unsaturated ...

17 Chapter 17Scheme 17.1. Pd‐catalyzed asymmetric allylic alkylation of α‐nitro esters wi...Scheme 17.2. (a) Enantio‐ and diastereoselective deracemization of cis‐2‐oxa...Scheme 17.3. Oxidative and redox neutral Pd‐catalyzed allylic arylation with...Scheme 17.4. Pd‐catalyzed asymmetric allylic alkylation with vinylcyclopropa...Scheme 17.5. Hydroxyacrylate nucleophiles in the Pd‐catalyzed asymmetric all...Scheme 17.6. Pd‐catalyzed DYKAT of benzylic diarylmethyl carbonates.Scheme 17.7. Asymmetric allylic alkylation with Mortia–Baylis–Hillman adduct...Scheme 17.8. Pd‐catalyzed asymmetric allylic fluoroalkylation of cyclic ally...Scheme 17.9. Dearomative C₂ selective allylic alkylation of pyrrole nucleoph...Scheme 17.10. Pd‐catalyzed asymmetric allylic alkylation of in situ generate...Scheme 17.11. Allylic alkylation of enols with allyl alcohol via CO₂ activat...Scheme 17.12. Cu/Pd dual catalysis for the asymmetric allylic alkylation of ...Scheme 17.13. Pd/Cu dual catalysis for enantio‐ and diastereodivergent allyl...Scheme 17.14. Merger of photoredox catalysis and Pd‐catalyzed enantioselecti...Figure 17.1. Enantioenriched motifs accessed by Stoltz via decarboxylative a...Figure 17.2. Substrate classes prepared via Pd‐catalyzed decarboxylative all...Scheme 17.15. Asymmetric decarboxylative propargylation of α‐aryl indanones....Scheme 17.16. Michael acceptor interrupted Pd‐catalyzed allylic alkylation....Scheme 17.17. Decarboxylative allylic alkylation of benzoxazolinone‐derived ...Scheme 17.18. (a) Acyclic stereocontrol in amides.(b) Acyclic stereocont...Scheme 17.19. Ni‐catalyzed asymmetric allylic alkylation of diarylmethanes a...Scheme 17.20. Ni‐catalyzed allylic alkylation of cyclic β‐ketoesters with un...Scheme 17.21. Ni‐catalyzed allylic alkylation of α‐acyl lactones with unacti...Scheme 17.22. Ni‐catalyzed allylic alkylation of cyclic β‐ketoesters with N‐...Scheme 17.23. Ni‐catalyzed allylic alkylation of acyclic acyl imidazoles wit...Scheme 17.24. Ni‐catalyzed Suzuki‐type cross‐coupling of pro‐quinolinium ele...Scheme 17.25. Mo‐catalyzed allylic alkylation of acyclic α‐cyanoesters.Scheme 17.26. (a) Cyclopentadienyl ruthenium complex catalyzed allylic alkyl...Scheme 17.27. (a) Rh‐catalyzed DYKAT of cyclic allylic bromides and chloride...Scheme 17.28. (a) Enantioselective Rh‐catalyzed allylic alkylation of acycli...Scheme 17.29. (a) Rh‐catalyzed allylic alkylation of 1,3‐diketones with ally...Scheme 17.30. (a) Ir‐catalyzed allylic alkylation of 3‐fluorosubstituted ele...Scheme 17.31. (a) First report of an MAC nucleophile in the Ir‐catalyzed all...Scheme 17.32. Counterion‐controlled diastereoselective Ir‐catalyzed allylic ...Scheme 17.33. (a) Diastereo‐ and enantioselective allylic alkylation of 5H‐o...Scheme 17.34. (a) Ir‐catalyzed allylic alkylation of cyclic β‐ketoesters. (b...Scheme 17.35. Ir‐catalyzed regio‐, diastereo‐, and enantioselective allylic ...Scheme 17.36. (a) Tandem Ir‐catalyzed allylic alkylation/Cope rearrangement....Scheme 17.37. Ir‐catalyzed enantioselective allylic alkylation with crotyl c...Scheme 17.38. Stereodivergent Ir‐catalyzed catalyzed allylic alkylation via ...Scheme 17.39. Ir‐catalyzed allylic alkylation of trimethylsiloxy furan.Scheme 17.40. Diastereo‐ and enantioselective allylic alkylation of non‐stab...Scheme 17.41. Dual‐catalytic stereodivergence in the Ir‐catalyzed allylic al...Scheme 17.42. Desymmetrizing CADA of bisphenol derivatives.Scheme 17.43. Allyl–olefin coupling via Ir‐catalyzed allylic substitution....Scheme 17.44. Ir‐catalyzed allylic alkylation with functionalized organozinc...Scheme 17.45. Formal umpolung allylation of N‐fluorenyl imines.Scheme 17.46. Cu‐catalyzed allylic alkylation of organolithium reagents.Scheme 17.47. (a) Cu‐catalyzed asymmetric allylic alkylation of allylic chlo...Scheme 17.48. (a) Enantioselective allylic arylation of allylic bromides to ...Scheme 17.49. (a) Enantioselective allylic alkylation of alkynylaluminum for...Scheme 17.50. Cu‐catalyzed enantioselective allylic alkylation with organobo...Scheme 17.51. Cu‐catalyzed asymmetric allylic allenylation with bench‐stable...Scheme 17.52. Cu‐catalyzed allylic alkylation of alkyl boranes with Z‐allyli...Scheme 17.53. Dynamic kinetic asymmetric allylic alkylation of alkylzirconiu...Scheme 17.54. Cu‐catalyzed allylic alkylation with terminal alkyne nucleophi...Scheme 17.55. Cu‐catalyzed allylic alkylation of formidyl cuprates.Scheme 17.56. Cu‐catalyzed enantioselective allylic alkylation of γ‐butyrola...Scheme 17.57. First example of a highly enantio‐ and regioselective Co‐catal...Scheme 17.58. Enantio‐ and regioselective Co‐catalyzed allylic alkylation of...Scheme 17.59. Organophotoredox approach to Co‐catalyzed enantioselective all...

18 Chapter 18Scheme 18.1. Carbometallation of alkynes and alkenes.Scheme 18.2. Asymmetric carbometallation of alkenes.Scheme 18.3. ZACA reactions of allyl alcohols.Scheme 18.4. ZACA reactions of tert‐butyldimethylsilyl‐protected terminal al...Scheme 18.5. ZACA reactions of unfunctionalized alkenes.Scheme 18.6. Zirconium‐catalyzed inter‐ and intramolecular double carboalumi...Scheme 18.7. Copper‐catalyzed carbometallation of cyclopropenes with vinylal...Scheme 18.8. Palladium‐catalyzed carbozincation of spirocyclopropenes.Scheme 18.9. Palladium‐catalyzed carbozincation of 3,3‐disubstituted cyclopr...Scheme 18.10. Copper‐catalyzed carbozincation of 3,3‐disubstituted cycloprop...Scheme 18.11. Copper‐catalyzed carbomagnesiation of 3,3‐disubstituted cyclop...Scheme 18.12. Copper‐catalyzed carbomagnesiation of 3,3‐disubstituted cyclop...Scheme 18.13. Palladium‐catalyzed and carbopalladation‐initiated carbocycliz...Scheme 18.14. Palladium‐catalyzed intramolecular carboiodination.Scheme 18.15. Palladium‐catalyzed intramolecular reductive Heck reactions.Scheme 18.16. Palladium‐catalyzed intramolecular arylative dearomatization o...Scheme 18.17. Palladium‐catalyzed intramolecular carboiodination‐isocyanide ...Scheme 18.18. Palladium‐catalyzed intramolecular reductive Heck reactions us...Scheme 18.19. Palladium‐catalyzed vinylborylation of (Z)‐1‐iododienes with b...Scheme 18.20. Palladium‐catalyzed arylalkynylation of indoles.Scheme 18.21. Palladium‐catalyzed dearomative arylborylation of indoles.Scheme 18.22. Palladium‐catalyzed intramolecular carbonylative Heck reaction...Scheme 18.23. Palladium‐catalyzed tandem intramolecular Heck insertion and T...Scheme 18.24. Palladium‐catalyzed Heck reactions of acyclic alkenyl fluoride...Scheme 18.25. Palladium‐catalyzed tandem Heck insertion and Sonogashira coup...Scheme 18.26. Palladium‐catalyzed hydroalkynylation of 3,3‐disubstituted cyc...Scheme 18.27. Nickel‐catalyzed intramolecular carboiodination of alkenes wit...Scheme 18.28. Nickel‐catalyzed intramolecular intramolecular Mizoroki–Heck c...Scheme 18.29. Nickel‐catalyzed intramolecular dearomative and reductive Heck...Scheme 18.30. Nickel‐catalyzed intramolecular carboiodination of alkenes wit...Scheme 18.31. Nickel‐catalyzed carbocyclization of tethered allene–ketone wi...Scheme 18.32. Rhodium‐catalyzed carborhodation of cyclopent‐2‐ene‐1,4‐diethy...Scheme 18.33. Rhodium‐catalyzed arylation of azabicyclic alkene with arylbor...Scheme 18.34. Rhodium‐catalyzed arylation of β‐Substituted alkenyl‐para‐nitr...Scheme 18.35. Rhodium‐catalyzed tandem ring‐opening and intramolecular C–O c...Scheme 18.36. Rhodium‐catalyzed arylation of 3,3‐disubstituted cyclopropenes...Scheme 18.37. Rhodium‐catalyzed arylation of 2H‐chromenes with aryl boronic ...Scheme 18.38. Rhodium‐catalyzed carbozincation of 1,6‐enynes with ArZnCl.Scheme 18.39. Cobalt‐catalyzed alkynylation of 1,1‐disubstituted allenes wit...Scheme 18.40. Cobalt‐catalyzed hydroborative cyclization of amide‐tethered 1...Scheme 18.41. Cobalt‐catalyzed hydroborative cyclization of anilide‐tethered...Scheme 18.42. Cobalt‐catalyzed hydroalkylation of oxabicyclic alkenes with c...

19 Chapter 19Scheme 19.1. Pd/DTB‐SIPE‐catalyzed asymmetric Suzuki‐Miyaura coupling.Scheme 19.2. Pd/BaryPhos‐catalyzed asymmetric Suzuki‐Miyaura cross‐coupling....Scheme 19.3. Electrochemical‐mediated Ni‐catalyzed reductive homo‐coupling....Scheme 19.4. Pd/chiral norbornene‐catalyzed three‐component coupling with va...Scheme 19.5. Pd‐catalyzed asymmetric intramolecular C‐H arylation.Scheme 19.6. Iridium‐catalyzed asymmetric intermolecular C‐H arylation.Scheme 19.7. Copper‐catalyzed asymmetric Michael‐type addition.Scheme 19.8. Recent achievements in direct asymmetric oxidative coupling of ...Scheme 19.9. Redox‐neutral coupling of azonaphthalenes with aryl alcohols or...Scheme 19.10. Rh‐catalyzed cycloisomerization reactions. (a) Access of axial...Scheme 19.11. Ir‐catalyzed asymmetric hydrogenation of bridged biaryl lacton...Scheme 19.12. Atroposelective ring‐opening reactions of cyclic diaryliodoniu...Scheme 19.13. Atroposelective C‐H functionalization with transient directing...Scheme 19.14. Redox‐neutral amination of phenol‐benzyl alcohols.Scheme 19.15. Atroposelective C‐H arylation of 1,2,3‐triazoles.Scheme 19.16. Asymmetric Paal‐Knorr reaction toward arylpyrrole atropisomers...Scheme 19.17. Asymmetric heteroannulation toward atropisomeric pyrrole deriv...Scheme 19.18. Rh‐catalyzed synthesis of 2,3′‐biindolyls.Scheme 19.19. Pd‐catalyzed cyclizative dimerization to form bisbenzothiophen...Scheme 19.20. Rh‐catalyzed oxidative olefination of benzo[h]isoquinolines....Scheme 19.21. Asymmetric hydrosilylation of heterobiaryl ketones.Scheme 19.22. DYKAT of stable heterobiaryl atropisomers. (a) General mechani...Scheme 19.23. Copper‐catalyzed asymmetric aryl amination.Scheme 19.24. Atroposelective Satoh‐Miura‐type reaction.Scheme 19.25. Axially chiral anilides generated from asymmetric C‐H olefinat...Scheme 19.26. Atroposelective intramolecular amination.Scheme 19.27. Asymmetric synthesis of 2‐aryl cyclohex‐2‐enone atropisomers....Scheme 19.28. Alkyne annulation in synthesis of axially chiral isoquinolones...Scheme 19.29. Atroposelective C–H functionalization of aryl alkenes. (a) Pal...Scheme 19.30. CPA‐catalyzed direct arylation of 2‐naphthols with quinones....Scheme 19.31. CPA‐catalyzed arylation of hydroxyarenes with N‐sulfonyl imino...Scheme 19.32. Aminocatalytic atroposelective arene‐forming aldol condensatio...Scheme 19.33. Organocatalytic construction of compounds with helical and axi...Scheme 19.34. Asymmetric (4+2) annulation of δ‐acetoxy allenoates and 2‐hydr...Scheme 19.35. Organocatalytic transesterification of Bringmann’s lactones....Scheme 19.36. Atropodivergent reductive amination of biaryl lactols.Scheme 19.37. Sequential DKR events catalyzed by peptide catalysts.Scheme 19.38. Desymmetrization and secondary kinetic resolution of biaryl am...Scheme 19.39. Organocatalyzed KR via N‐functionalization.Scheme 19.40. Organocatalyzed KR of BINOLs via O‐functionalization. (a) Isot...Scheme 19.41. Heteroatropisomers formed from organocatalytic arylation.Scheme 19.42. Coupling of aromatic alcohols and electrophilic 2‐indolylmetha...Scheme 19.43. N‐heterobiaryl atropisomers formed from annulation‐oxidative a...Scheme 19.44. Asymmetric construction of 3‐arylpyrroles. (a) Asymmetric Bart...Scheme 19.45. CPA‐catalyzed three‐component heteroannulation.Scheme 19.46. Atroposelective synthesis of N‐aryl benzimidazoles.Scheme 19.47. Furan atropisomers from β‐naphthyl nitroolefin and C/O‐bi...Scheme 19.48. NHC‐catalyzed synthesis of benzofuran‐ and indole‐derived brid...Scheme 19.49. Asymmetric addition to form axially chiral 3,3′‐bisindoles....Scheme 19.50. Atroposelective halogenation of 8‐arylquinolines.Scheme 19.51. CPA‐catalyzed desymmetrization of N‐phenylpyrroles.Scheme 19.52. Atroposelective C‐H amination of N‐aryl‐2‐naphthylamines.Scheme 19.53. CPA‐catalyzed asymmetric synthesis of N‐arylquinazolinones....Scheme 19.54. Atroposelective synthesis of spirobenzazepinones.Scheme 19.55. Asymmetric allylic alkylation of anilides.Scheme 19.56. Peptide‐catalyzed asymmetric bromination of quinazolinones....Scheme 19.57. Atroposelective halogenation of N‐aryl quinoids.Scheme 19.58. Desymmetrization of N‐(2‐tert‐butylphenyl)maleimides and ATADs...Scheme 19.59. Aromatic amides from arene‐forming aldol condensation.Scheme 19.60. DKR of atropisomeric amides enabled by transition‐state hydrog...Scheme 19.61. Atroposelective synthesis of axially chiral arylquinones.Scheme 19.62. NHC‐catalyzed asymmetric [3+3]‐annulation.Scheme 19.63. Chiral sulfide‐catalyzed electrophilic carbothiolation of alky...Scheme 19.64. Organocatalytic Michael addition of alkynals.Scheme 19.65. Asymmetric synthesis of aryl‐alkene‐indoles.Scheme 19.66. Synthesis of atropochiral styrenes via VQM intermediate. (a) G...Scheme 19.67. Enantioenriched alkene atropisomers from atroposelective funct...Scheme 19.68. Ru‐complex and lipase co‐mediated DKR of biaryls.Scheme 19.69. Biocatalytic aldehyde reduction.

20 Chapter 20Scheme 20.1. Representatives of planar chiral molecules.Scheme 20.2. Characteristics of carbohelicenes.Scheme 20.3. Enantioselective lithiation of ferrocenes using chiral amines....Scheme 20.4. Intramolecular reaction of diazo compounds.Scheme 20.5. C–H arylation using aryl boronic acids directed by an aminometh...Scheme 20.6. C–H alkenylation using alkenes directed by an aminomethyl group...Scheme 20.7. C–H annulation using diaryl alkynes directed by an aminomethyl ...Scheme 20.8. C–H acylation using 1,2‐diketones directed by an aminomethyl gr...Scheme 20.9. C–H/C–H coupling using (benzo)heteroles directed by an aminomet...Scheme 20.10. C–H/C–H coupling using heteroles directed by an aminomethyl gr...Scheme 20.11. C–H arylation using iodoarenes directed by a carbonyl group....Scheme 20.12. C–H alkenylation using alkenes directed by a carboxyl group....Scheme 20.13. C–H alkylation using alkenes directed by an isoquinolyl group....Scheme 20.14. C–H alkenylation using alkynes by a quinolyl group.Scheme 20.15. C–H amidation using 1,4,2‐dioxazol‐5‐ones directed by a pyridy...Scheme 20.16. C–H amidation using 1,4,2‐dioxazol‐5‐ones directed by a thioam...Scheme 20.17. C–H amidation using 1,4,2‐dioxazol‐5‐ones directed by an amide...Scheme 20.18. C–H arylation using haloarenes directed by a pyridyl group....Scheme 20.19. C–H arylation using iodoarenes directed by a thiocarbonyl grou...Scheme 20.20. Intramolecular C–H arylation using carbonyl‐tethered haloarene...Scheme 20.21. Intramolecular C–H arylation using carbonyl‐tethered halopyrid...Scheme 20.22. Intramolecular C–H arylation using amide‐tethered haloarenes....Scheme 20.23. Intramolecular C–H arylation using amide‐tethered bromoarenes....Scheme 20.24. Intramolecular C–H arylation using sulfide‐tethered bromoarene...Scheme 20.25. C–H annulation of isocyanides using haloarenes.Scheme 20.26. C–H annulation of alkynyl amides using iodoarenes.Scheme 20.27. Intramolecular C–H/Si–H coupling.Scheme 20.28. Inter‐ and intramolecular dehydrogenative couplings of diethyl...Scheme 20.29. C–H annulation of a carboxamide using an alkyne.Scheme 20.30. C–H annulation of formamides using alkynes.Scheme 20.31. Cycloisomerization of ortho‐phenylene‐tethered alkynes.Scheme 20.32. Cycloisomerization of ortho‐phenylene‐tethered propargylamines...Scheme 20.33. Desymmetric Suzuki coupling of a dichloroarene chromium comple...Scheme 20.34. Desymmetric intramolecular Heck reaction of 1,3‐diallyl chromi...Scheme 20.35. Desymmetric reduction and Suzuki coupling of a 5,8‐dibromonaph...Scheme 20.36 Desymmetric intramolecular metathesis of 1,3‐diisoproneyl chrom...Scheme 20.37. Intramolecular cycloaddition of triynes for the synthesis of m...Scheme 20.38. Intermolecular cycloaddition of diynes for the synthesis of me...Scheme 20.39. Intermolecular cycloaddition of diynes for the synthesis of pa...Scheme 20.40. Intermolecular cycloaddition of cyclic diynes for the synthesi...Scheme 20.41. Intramolecular cycloaddition for the construction of annulated...Scheme 20.42. Intramolecular cycloaddition for the construction of zigzag‐ty...Scheme 20.43. Intramolecular cycloaddition of triynes for the synthesis of t...Scheme 20.44. Intramolecular cycloaddition of diyne‐nitriles for the synthes...Scheme 20.45. Inter‐ and intramolecular cross‐couplings of dibromides with d...Scheme 20.46. Consecutive Sonogashira couplings of 2,5‐diiodo‐1,4‐dixoa[n]pa...Scheme 20.47. Enantioselective lithiation of dioxa[n]paracyclophanes using a...Scheme 20.48. Intramolecular S_N2 reaction for the synthesis of cyclic trans‐...Scheme 20.49. Intramolecular allylic amination for the synthesis of cyclic t...Scheme 20.50. Intramolecular cycloaddition of a triyne for the synthesis of ...Scheme 20.51. Intramolecular cycloaddition of triynes for the synthesis of c...Scheme 20.52. Intramolecular cycloaddition of a triyne for the synthesis of ...Scheme 20.53. Intramolecular cycloaddition of triynes for the synthesis of d...Scheme 20.54. Intermolecular cycloaddition of a benzyne precursor for the sy...Scheme 20.55. Consecutive intramolecular cycloaddition of hexaynes for the s...Scheme 20.56. Intramolecular cycloaddition of triynes for the synthesis of o...Scheme 20.57. Consecutive intramolecular cycloaddition of a hexayne for the ...Scheme 20.58. Consecutive intramolecular cycloaddition of a hexayne for the ...Scheme 20.59. Consecutive intramolecular cycloaddition of a polyne for the s...Scheme 20.60. Intermolecular cycloaddition of tetraynes with diynes for the ...Scheme 20.61. Intermolecular cycloaddition of a tetrayne with a diyne for th...Scheme 20.62. Intermolecular cycloaddition of a hexayne with a diyne for the...Scheme 20.63. Intermolecular cycloaddition of tetraynes with diynes for the ...Scheme 20.64. Consecutive cycloisomerization of tetraynes for the preparatio...Scheme 20.65. Consecutive cycloisomerization of tetraynes for the preparatio...Scheme 20.66 Consecutive cycloisomerization of tetraynes for the preparation...Scheme 20.67. Consecutive cycloisomerization of diynes for the synthesis of ...Scheme 20.68 Cycloisomerization of alkynes for the synthesis of disubstitute...Scheme 20.69. Cycloisomerization of alkynes for the synthesis of substituted...Scheme 20.70 Consecutive cycloisomerization of diynes for the synthesis of c...Scheme 20.71. Condensation of fused‐cyclohexanones with arylhyrazines for th...Scheme 20.72. Oxidative homo‐coupling of arenols for the synthesis of oxa[9]...Scheme 20.73. C–H annulation of 1‐arylisoquinolines with alkynes for the syn...

21 Chapter 21Scheme 21.1 Enantioselective polymerization of various racemic monosubstitut...Scheme 21.2 Monomers and ligands used in asymmetric anionic polymerization o...Scheme 21.3 Divinyl monomer and catalysts used in enantioselective cyclopoly...Scheme 21.4 Stereospecific polymerization of cyclic olefins, and employed li...Scheme 21.5 Chiral ligands used in asymmetric alternating copolymerization o...Scheme 21.6 Enantioselective resolution homopolymerization of propylene oxid...Scheme 21.7 Catalysts used in asymmetric copolymerization of meso‐epox...Scheme 21.8 Intramolecular bimetallic mechanism for enantioselective polymer...Scheme 21.9 Asymmetric copolymerization of cyclohexane epoxide with COS medi...Scheme 21.10 Various catalysts involved in enantioselective polymerization o...Scheme 21.11 Kinetic resolution polymerization of racemic eight‐membered cyc...Scheme 21.12 Asymmetric copolymerization of various meso‐epoxides with cycli...Scheme 21.13 Enantioselective resolution copolymerization of racemic termina...Scheme 21.14 Asymmetric condensation polymerization.Scheme 21.15 Asymmetric oxidative‐coupling polymerization of 2,3‐dihudroxyna...

22 Chapter 22Figure 22.1. Classification of flow reactions in fine organic synthesis.Figure 22.2. Batch method and continuous‐flow method – from the viewpoint of...Figure 22.3. Type IV continuous‐flow enantioselective 1,4‐addition with poly...Figure 22.4 Type III continuous‐flow enantioselective 1,4‐addition and catal...Figure 22.5 Sequential continuous‐flow synthesis of the baclofen precursor....Figure 22.6. Mesoporous silica/Ni–diamine composite for continuous‐flow synt...Figure 22.7. Polymer‐bound nickel–diamine catalyst for continuous‐flow 1,4‐a...Figure 22.8. Immobilized organocatalytic continuous‐flow 1,4‐addition reacti...Figure 22.9. Continuous‐flow enantioselective 1,4‐addition reaction of aldeh...Figure 22.10. Continuous‐flow enantioselective 1,4‐addition reaction of alde...Figure 22.11. Hydroxyquinone 1,4‐addition to nitrostyrene.Figure 22.12. Continuous‐flow 1,4‐addition of ketone to nitroolefin.Figure 22.13. Quinine/benzoic acid bifunctional catalysis for enantioselecti...Figure 22.14. CPA‐containing MOF‐catalyzed enantioselective 1,4‐addition of ...Figure 22.15. Amphiphilic resin‐supported chiral diene Rh complex.Figure 22.16. Ligand–Rh/Ag nanoparticle Co‐immobilization system for continu...Figure 22.17. Asymmetric Robinson annulation.Figure 22.18. Continuous‐flow Aldol reaction with a homogeneous catalyst‐pac...Figure 22.19. Asymmetric organocatalytic Aldol reaction (Type III) in hydrop...Figure 22.20. Silica‐immobilized H8‐BINOL as a catalyst for organo‐titanium ...Figure 22.21. Polystyrene‐supported cinchona alkaloid‐derived thiourea catal...Figure 22.22. Porous carbon nanosheet/polymer hybrid‐supported chiral squara...Figure 22.23. Continuous‐flow enantioselective Henry reaction with Nd/Na het...Figure 22.24. Continuous‐flow enantioselective Strecker‐type reaction with c...Figure 22.25. Continuous‐flow hydrocyanation reaction with immobilized enzym...Figure 22.26. Type IV continuous‐flow enantioselective Mannich reaction inte...Figure 22.27. Continuous‐flow asymmetric allylboration with polymer‐supporte...Figure 22.28. Chiral NHC catalysis under continuous‐flow conditions.Figure 22.29. Continuous‐flow enantioselective Diels–Alder reaction using im...Figure 22.30. Optimization of Type III continuous‐flow reaction with the ass...Figure 22.31. Homochiral cage catalyst for continuous‐flow enantioselective ...Figure 22.32. Anchor effects in organocatalytic enantioselective cyclopropan...Figure 22.33. Continuous‐flow enantioselective C–H insertion reaction with s...Figure 22.34. Type III continuous‐flow asymmetric hydroformylation.Figure 22.35. Heterogeneous Rh catalyst immobilized on carbon by π–π interac...Figure 22.36. Continuous‐flow enantioselective α‐amination of oxindole.Figure 22.37. Photopolymerized chiral monolithic chip reactor for continuous...Figure 22.38. Type IV continuous‐flow enantioselective electrophilic fluorin...Figure 22.39. Type III continuous‐flow enantioselective electrophilic fluori...Figure 22.40. Type III continuous‐flow enantioselective photooxygenation of ...Figure 22.41. Continuous‐flow enantioselective electrochemical process.Figure 22.42. Type III continuous‐flow enantioselective sulfoxidation.Figure 22.43. Continuous‐flow kinetic resolution of racemic alcohol.Figure 22.44. Supported isothiourea catalyst in continuous‐flow kinetic reso...Figure 22.45. Continuous‐flow desymmetrization with immobilized chiral SPINO...Figure 22.46. Type III Corey–Bakshi–Shibata reductions in a microreactor sys...Figure 22.47. Type III organocatalytic enantioselective reductions of nitroe...Figure 22.48. Type III continuous‐flow asymmetric transfer hydrogenation inv...Figure 22.49. Continuous‐flow enantioselective MPV‐type reduction with suppo...Figure 22.50. Enantioselective hydrogenation of imines using supported Ir/no...Figure 22.51. Continuous‐flow organocatalytic enantioselective hydrosilylati...Figure 22.52. Supported rhodium‐catalyzed Type IV continuous‐flow enantiosel...Figure 22.53. Supported rhodium‐catalyzed Type IV continuous‐flow enantiosel...Figure 22.54. Modified Augustine approach for continuous‐flow enantioselecti...Figure 22.55. Assembling catalytic functions into single heterogeneous mater...