Diazomethane → HCID 59279850, compound

HRID 1875384Notes

Reaction equation

HRID 1875384 reaction equation
[N+](=[CH2:3])=[N-].[CH2:4]([O:6][C:7]1[CH:16]=[C:15]([O:17][C@H:18]2[CH2:22][N:21]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[C@H:20]([C:30]([O:32][CH3:33])=[O:31])[CH2:19]2)[C:14]2[C:9](=[CH:10][C:11]([O:42][CH3:43])=[C:12](/[CH:34]=[CH:35]/[CH2:36][C:37]([CH3:41])([CH3:40])[CH2:38][OH:39])[CH:13]=2)[N:8]=1)[CH3:5]>CCOCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:4]([O:6][C:7]1[CH:16]=[C:15]([O:17][C@H:18]2[CH2:22][N:21]([C:23]([O:25][C:26]([CH3:28])([CH3:29])[CH3:27])=[O:24])[C@H:20]([C:30]([O:32][CH3:33])=[O:31])[CH2:19]2)[C:14]2[C:9](=[CH:10][C:11]([O:42][CH3:43])=[C:12]([CH:34]3[CH2:3][CH:35]3[CH2:36][C:37]([CH3:41])([CH3:40])[CH2:38][OH:39])[CH:13]=2)[N:8]=1)[CH3:5]

Participants

5

Reactant 2

HCID 9550Diazomethane3×HCID 59279991HCID 59279991, compound

Product 1

HCID 59279850HCID 59279850, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalyst3×HCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

Palladium acetate (0.67 g, 2.97 mol) and freshly prepared diazomethane (300 mL, 0.5 M solution in Et2O, 150 mmol) were added to a solution of the product from Step 3 (16.6 g, 29.7 mmol) in Et2O (300 mL) cooled to 0° C. After 15 minutes, N2 was bubbled through the mixture for 15 minutes, and the black mixture was filtered through CELITE with Et2O as the eluent. The solvent was removed in vacuo, and the residue was taken up in Et2O (300 mL) and cooled to 0° C. Palladium acetate (0.67 g, 2.97 mol) and freshly prepared diazomethane (100 mL, 0.5 M solution in Et2O, 50 mmol) were then added. After 15 minutes, N2 was bubbled through the mixture for 15 minutes, and the black mixture was filtered through CELITE with Et2O as the eluent. The solvent was removed in vacuo, and the residue was taken up in Et2O (300 mL) and cooled to 0° C. Palladium acetate (0.67 g, 2.97 mol) and freshly prepared diazomethane (100 mL, 0.5 M solution in Et2O, 50 mmol) were then added. After 15 minutes, N2 was bubbled through the mixture for 15 minutes, and the black mixture was filtered through CELITE with Et2O as the eluent. The solvent was removed in vacuo, and the crude product was purified on silica (gradient elution, 0-60% EtOAc/hexanes) to yield the title compound. LRMS ESI+ (M+H)+ 573.2, calcd for C31H45N2O8: 573.3.

Workup

  1. customN2 was bubbled through the mixture for 15 minutes
  2. filtrationthe black mixture was filtered through CELITE with Et2O as the eluent
  3. customThe solvent was removed in vacuo
  4. temperaturecooled to 0° C
  5. waitAfter 15 minutes
  6. customN2 was bubbled through the mixture for 15 minutes
  7. filtrationthe black mixture was filtered through CELITE with Et2O as the eluent
  8. customThe solvent was removed in vacuo
  9. temperaturecooled to 0° C
  10. waitAfter 15 minutes
  11. customN2 was bubbled through the mixture for 15 minutes
  12. filtrationthe black mixture was filtered through CELITE with Et2O as the eluent
  13. customThe solvent was removed in vacuo
  14. customthe crude product was purified on silica (gradient elution, 0-60% EtOAc/hexanes)

Sources & evidence

ORD record
ord-32369198cf374e57b5f889906f6935e1
Source dataset
uspto-grants-2012_11
Patent number
US08309540B2

Reaction notes

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