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