Catalytic Asymmetric Synthesis

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 C 1‐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(sp 3)–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....