Catalytic Asymmetric Synthesis

2 Chapter 5TABLE 5.1. Asymmetric α‐oxyaminaton of aldehyde and its variation.TABLE 5.2. Effect of helical part of peptide catalyst for enantioselective Fr...

3 Chapter 12TABLE 12.1. C–H insertion into doubly allylic sites.TABLE 12.2. C–H insertion of THF.TABLE 12.3. C–H insertion of 1‐methoxybutane.TABLE 12.4. Synthesis of β‐lactones.TABLE 12.5. C–H amidation of indane and tetraline.TABLE 12.6. Synthesis of cyclic sulfamidates with iminoiodinane.TABLE 12.7. Intermolecular C–H amination with azides.TABLE 12.8. Synthesis of arylsulfonamides.TABLE 12.9. Synthesis of pyrrolidines.TABLE 12.10. Synthesis of sulfamides and sulfonamides.TABLE 12.11. Stereoselective C–H amination with N ‐(sulfonyloxy)carbamates....TABLE 12.12. Synthesis of γ‐lactams.

4 Chapter 21TABLE 21.1. Binary catalyst systems based on chiral salenCo(III)X for racemi ...

1 Chapter 1 Figure 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 2 Figure 2.1. Examples of chiral Brønsted acids. Figure 2.2. p K avalues 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‐4 H ‐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 Rh 2(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 Rh 2(OAc) 4.