N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

Joseane A. Mendes,
Paulo R. R. Costa,
Miguel Yus,
Francisco Foubelo and
Camilla D. Buarque

Review
Published 12 May 2021

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1. Graphical Abstract
2. Scheme 1: General strategy for the enantioselective synthesis of N-containing heterocycles from N-tert-butane...
  
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3. Scheme 2: Methodologies for condensation of aldehydes and ketones with tert-butanesulfinamides (1).
  
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4. Scheme 3: Transition models for cis-aziridines and trans-aziridines.
  
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5. Scheme 4: Mechanism for the reduction of N-tert-butanesulfinyl imines.
  
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6. Scheme 5: Transition models for the addition of organomagnesium and organolithium compounds to N-tert-butanes...
  
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7. Scheme 6: Synthesis of 2,2-dibromoaziridines 15 from aldimines 14 and bromoform, and proposed non-chelation-c...
  
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8. Scheme 7: Diastereoselective synthesis of aziridines from tert-butanesulfinyl imines.
  
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9. Scheme 8: Synthesis of vinylaziridines 22 from aldimines 14 and 1,3-dibromopropene 23, and proposed chelation...
  
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10. Scheme 9: Synthesis of vinylaziridines 27 from aldimines 14 and α-bromoesters 26, and proposed transition sta...
  
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11. Scheme 10: Synthesis of 2-chloroaziridines 28 from aldimines 14 and dichloromethane, and proposed transition s...
  
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12. Scheme 11: Synthesis of cis-vinylaziridines 30 and 31 from aldimines 14 and bromomethylbutenolide 29.
  
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13. Scheme 12: Synthesis of 2-chloro-2-aroylaziridines 36 and 32 from aldimines 14, arylnitriles 34, and silyldich...
  
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14. Scheme 13: Synthesis of trifluoromethylaziridines 39 and proposed transition state of the aziridination.
  
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15. Scheme 14: Synthesis of aziridines 42 and proposed state transition.
  
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16. Scheme 15: Synthesis of 1-substituted 2-azaspiro[3.3]heptanes, 1-phenyl-2-azaspiro[3.4]octane and 1-phenyl-2-a...
  
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17. Scheme 16: Synthesis of 1-substituted 2,6-diazaspiro[3.3]heptanes 48 from chiral imines 14 and 1-Boc-azetidine...
  
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18. Scheme 17: Synthesis of β-lactams 52 from chiral imines 14 and dimethyl malonate (49).
  
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19. Scheme 18: Synthesis of spiro-β-lactam 57 from chiral (R_S)-N-tert-butanesulfinyl isatin ketimine 53 and ethyl ...
  
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20. Scheme 19: Synthesis of β-lactam 60, a precursor of (−)-batzelladine D (61) and (−)-13-epi-batzelladine D (62)...
  
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21. Scheme 20: Rhodium-catalyzed asymmetric synthesis of 3-substituted pyrrolidines 66 from chiral imine (R_S)-63 a...
  
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22. Scheme 21: Asymmetric synthesis of 1,3-disubstituted isoindolines 69 and 70 from chiral imine 67.
  
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23. Scheme 22: Asymmetric synthesis of cis-2,5-disubstituted pyrrolidines 73 from chiral imine (R_S)-71.
  
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24. Scheme 23: Asymmetric synthesis of 3-hydroxy-5-substituted pyrrolidin-2-ones 77 from chiral imine (R_S)-74.
  
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25. Scheme 24: Asymmetric synthesis of 4-hydroxy-5-substituted pyrrolidin-2-ones 80 from chiral imines 79.
  
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26. Scheme 25: Asymmetric synthesis of 3-pyrrolines 82 from chiral imines 14 and ethyl 4-bromocrotonate (81).
  
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27. Scheme 26: Asymmetric synthesis of γ-amino esters 84, and tetramic acid derivative 86 from chiral imines (R_S)-...
  
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28. Scheme 27: Asymmetric synthesis of α-methylene-γ-butyrolactams 90 from chiral imines (Z,S_S)-87 and ethyl 2-bro...
  
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29. Scheme 28: Asymmetric synthesis of methylenepyrrolidines 92 from chiral imines (R_S)-14 and 2-(trimethysilylmet...
  
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30. Scheme 29: Synthesis of dibenzoazaspirodecanes from cyclic N-tert-butanesulfinyl imines.
  
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31. Scheme 30: Stereoselective synthesis of cyclopenta[c]proline derivatives 103 from β,γ-unsaturated α-amino acid...
  
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32. Scheme 31: Stereoselective synthesis of alkaloids (−)-angustureine (107) and (−)-cuspareine (108).
  
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33. Scheme 32: Stereoselective synthesis of alkaloids (−)-pelletierine (112) and (+)-coniine (117).
  
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34. Scheme 33: Synthesis of piperidine alkaloids (+)-dihydropinidine (122a), (+)-isosolenopsin (122b) and (+)-isos...
  
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35. Scheme 34: Stereoselective synthesis of the alkaloids(+)-sedamine (125) from chiral imine (S_S)-119.
  
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36. Scheme 35: Stereoselective synthesis of trans-5-hydroxy-6-substituted-2-piperidinones 127 and 129 from chiral ...
  
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37. Scheme 36: Stereoselective synthesis of trans-5-hydroxy-6-substituted ethanone-2-piperidinones 132 from chiral...
  
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38. Scheme 37: Stereoselective synthesis of trans-3-benzyl-5-hydroxy-6-substituted-2-piperidinones 136 from chiral...
  
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39. Scheme 38: Stereoselective synthesis of trans-5-hydroxy-6-substituted 2-piperidinones 139 from chiral imine 138...
  
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40. Scheme 39: Stereoselective synthesis of ʟ-hydroxypipecolic acid 145 from chiral imine 144.
  
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41. Scheme 40: Synthesis of 1-substituted isoquinolones 147, 149 and 151.
  
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42. Scheme 41: Stereoselective synthesis of 3-substituted dihydrobenzo[de]isoquinolinones 154.
  
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43. Scheme 42: Enantioselective synthesis of alkaloids (S)-1-benzyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline (...
  
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44. Scheme 43: Enantioselective synthesis of alkaloids (−)-cermizine B (171) and (+)-serratezomine E (172) develop...
  
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45. Scheme 44: Stereoselective synthesis of (+)-isosolepnosin (177) and (+)-solepnosin (178) from homoallylamine d...
  
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46. Scheme 45: Stereoselective synthesis of tetrahydroquinoline derivatives 184, 185 and 187 from chiral imines (R_S...
  
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47. Scheme 46: Stereoselective synthesis of pyridobenzofuran and pyridoindole derivatives 193 from homopropargylam...
  
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48. Scheme 47: Stereoselective synthesis of 2-substituted 1,2,5,6-tetrahydropyridines 196 from chiral imines (R_S)-...
  
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49. Scheme 48: Stereoselective synthesis of 2-substituted trans-2,6-disubstituted piperidine 199 from chiral imine...
  
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50. Scheme 49: Stereoselective synthesis of cis-2,6-disubstituted piperidines 200, and alkaloid (+)-241D, from chi...
  
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51. Scheme 50: Stereoselective synthesis of 6-substituted piperidines-2,5-diones 206 and 1,7-diazaspiro[4.5]decane...
  
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52. Scheme 51: Stereoselective synthesis of spirocyclic oxindoles 210 from chiral imines (R_S)-53.
  
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53. Scheme 52: Stereoselective synthesis of azaspiro compound 213 from chiral imine 211.
  
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54. Scheme 53: Stereoselective synthesis of tetrahydroisoquinoline derivatives from chiral imines (R_S)-214.
  
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55. Scheme 54: Stereoselective synthesis of (−)-crispine A 223 from chiral imine (R_S)-214.
  
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56. Scheme 55: Synthesis of (−)-harmicine (228) using tert-butanesulfinamide through haloamide cyclization.
  
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57. Scheme 56: Stereoselective synthesis of tetraponerines T1–T8.
  
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58. Scheme 57: Stereoselective synthesis of phenanthroindolizidines 246a and (−)-tylophorine (246b), and phenanthr...
  
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59. Scheme 58: Stereoselective synthesis of indoline, tetrahydroquinoline and tetrahydrobenzazepine derivatives 253...
  
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60. Scheme 59: Stereoselective synthesis of (+)-epohelmin A (258) and (+)-epohelmin B (260) from aldimine (R_S)-79.
  
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61. Scheme 60: Stereoselective synthesis of (−)-epiquinamide (266) from chiral aldimine (S_S)-261.
  
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62. Scheme 61: Synthesis synthesis of (–)-hippodamine (273) and (+)-epi-hippodamine (272) using chiral sulfinyl am...
  
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63. Scheme 62: Stereoselective synthesis of (+)-grandisine D (279) and (+)-amabiline (283).
  
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64. Scheme 63: Stereoselective synthesis of (−)-epiquinamide (266) and (+)-swaisonine (291) from aldimine (S_S)-126....
  
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65. Scheme 64: Stereoselective synthesis of (+)-C(9a)-epi-epiquinamide (294).
  
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66. Scheme 65: Stereoselective synthesis of (+)-lasubine II (298) from chiral aldimine (S_S)-109.
  
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67. Scheme 66: Stereoselective synthesis of (−)-epimyrtine (300a) and (−)-lasubine II (ent-302) from β-amino keton...
  
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68. Scheme 67: Stereoselective synthesis of (−)-tabersonine (310), (−)-vincadifformine (311), and (−)-aspidospermi...
  
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69. Scheme 68: Stereoselective synthesis of (+)-epohelmin A (258) and (+)-epohelmin B (260) from aldehyde 313 and ...
  
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70. Scheme 69: Total synthesis of (+)-lysergic acid (323) from N-tert-butanesulfinamide (RS)-1.
  
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