Catalytic Asymmetric Synthesis

3 Chapter 3 Figure 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 5 H ‐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 28 Figure 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 )‐34 Scheme 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 4 Scheme 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...