Tetrahydrofuran → HCID 131727747, compound

HRID 1434473Notes

Reaction equation

HRID 1434473 reaction equation
[CH2:1]([O:48][CH:49]1[C@H:53]2[C@H:54](O[Si](C(C)(C)C)(C)C)[N:55](C(OCC(Cl)(Cl)Cl)=O)[C:56]3[CH:63]=[CH:62][C:61]([O:64][CH3:65])=[CH:60][C:57]=3[C:58](=[O:59])[N:52]2[CH:51]=[C:50]1[C:82]1[CH:87]=[CH:86][C:85]([O:88][CH3:89])=[CH:84][CH:83]=1)[CH2:2][CH2:3][CH2:4][CH2:5][O:6][CH:7]1[C@H:11]2[C@H:12](O[Si](C(C)(C)C)(C)C)[N:13](C(OCC(Cl)(Cl)Cl)=O)[C:14]3[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][C:15]=3[C:16](=[O:17])[N:10]2[CH:9]=[C:8]1[C:40]1[CH:45]=[CH:44][C:43]([O:46][CH3:47])=[CH:42][CH:41]=1.C1COCC1>C(Cl)(Cl)Cl.CO>[CH2:1]([O:48][CH:49]1[C@@H:53]2[CH:54]=[N:55][C:56]3[CH:63]=[CH:62][C:61]([O:64][CH3:65])=[CH:60][C:57]=3[C:58](=[O:59])[N:52]2[CH:51]=[C:50]1[C:82]1[CH:83]=[CH:84][C:85]([O:88][CH3:89])=[CH:86][CH:87]=1)[CH2:2][CH2:3][CH2:4][CH2:5][O:6][CH:7]1[C@@H:11]2[CH:12]=[N:13][C:14]3[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][C:15]=3[C:16](=[O:17])[N:10]2[CH:9]=[C:8]1[C:40]1[CH:41]=[CH:42][C:43]([O:46][CH3:47])=[CH:44][CH:45]=1

Participants

4

Reactant 2

HCID 8028TetrahydrofuranHCID 131727745HCID 131727745, compound

Product 1

HCID 131727747HCID 131727747, compoundYield 55%

Reagents, catalysts & solvents 1

HCID 21584188Chloroform methanolSolvent

Procedure

10% Cd/Pb couple (192 mg, 1.55 mmol) was added to a rapidly stirring mixture of 45 (107 mg, 77.3 μmol), THF (2.5 mL) and 1N NH4OAc (2.5 mL). The reaction mixture was allowed to stir for 3 hours at which point TLC (95:5 v/v CHCl3/MeOH) showed the formation of desired PBD accompanied by side-products. The solids were collected by filtration and rinsed with H2O and DCM. The aqueous layer was extracted with DCM (3×10 mL) and the organic extracts were combined, washed with brine (50 mL) and dried (MgSO4). Filtration and evaporation of solvent afforded the crude product which was purified by flash column chromatography (gradient elution: CHCl3 to 99:1 v/v CHCl3/MeOH) to afford the imine 46 as a yellow glass (32.5 mg, 55%): 1H NMR (400 MHz, CDCl3) δ 7.89 (d, 2H, J=3.9 Hz), 7.53 (s, 2H), 7.39 (s, 2H), 7.34 (d, 4H, J=8.8 Hz), 6.90 (d, 4H, J=8.8 Hz), 6.82 (s, 2H), 4.43-4.38 (m, 2H), 4.18-4.05 (m, 4H), 3.95 (s, 6H), 3.83 (s, 6H), 3.58 (ddd, 2H, J=16.2, 11.5, 1.9 Hz), 3.38 (ddd, 2H, J=16.3, 5.1, 1.6 Hz), 2.01-1.94 (m, 4H), 1.73-1.66 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 162.6, 161.3, 159.2, 151.3, 148.1, 140.3, 126.2, 126.0 (×2), 123.2, 122.0, 119.1, 114.3, 111.9, 110.9, 68.8, 56.2, 55.4, 53.9, 35.6, 28.7, 22.6.

Workup

  1. filtrationThe solids were collected by filtration
  2. washrinsed with H2O and DCM
  3. extractionThe aqueous layer was extracted with DCM (3×10 mL)
  4. washwashed with brine (50 mL)
  5. dry with materialdried (MgSO4)
  6. filtrationFiltration and evaporation of solvent
  7. customafforded the crude product which
  8. customwas purified by flash column chromatography (gradient elution: CHCl3 to 99:1 v/v CHCl3/MeOH)

Sources & evidence

ORD record
ord-0033bd1733ec465d8ab89707c11e25a7
Source dataset
uspto-grants-2009_11
Patent number
US07612062B2

Reaction notes

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