Trifluoromethanesulfonic anhydride → HCID 57309348, compound

HRID 235772Notes

Reaction equation

HRID 235772 reaction equation
O=[C:2]1[CH2:8][C@H:7]2[N:4]([C:5](=[O:14])[C@H:6]2[C:9]([O:12][CH3:13])([CH3:11])[CH3:10])[C@H:3]1[C:15]([O:17][CH2:18][C:19]1[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][CH:20]=1)=[O:16].C(N(C(C)C)CC)(C)C.FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.[N:52]1[CH:57]=[CH:56][C:55]([SH:58])=[CH:54][CH:53]=1>CN(C1C=CN=CC=1)C.C(Cl)Cl.CN(C)C=O>[CH3:13][O:12][C:9]([C@@H:6]1[C:5](=[O:14])[N:4]2[C@@H:7]1[CH2:8][C:2]([S:58][C:55]1[CH:56]=[CH:57][N:52]=[CH:53][CH:54]=1)=[C:3]2[C:15]([O:17][CH2:18][C:19]1[CH:20]=[CH:21][C:22]([N+:25]([O-:27])=[O:26])=[CH:23][CH:24]=1)=[O:16])([CH3:11])[CH3:10]

Participants

8

Reactant 4

HCID 67749Trifluoromethanesulfonic anhydride2×HCID 81531Diisopropylethylamine3×HCID 86741286HCID 86741286, compoundHCID 178418431pyridine-4-thiol

Product 1

HCID 57309348HCID 57309348, compoundYield 67.5%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalyst2×HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent6×

Procedure

To a solution of 4-nitrobenzyl (2R, 5R, 6R)-3,7-dioxo-6-(1-methoxy-1-methylethyl)-1-azabicyclo[3.2.0]heptane-2-carboxylate (450 mg) and 4-(N,N-dimethylamino)pyridine (14.6 mg) in methylene chloride (22.5 ml) was added a solution of N,N-diisopropyl-N-ethylamine (0.249 ml) in methylene chloride (2.241 ml) at -30° C. To the mixture was added further a solution of trifluoromethanesulfonic anhydride (0.211 ml) in methylene chloride (1.899 ml) at -30° C. After stirring for 30 minutes at the same temperature, a solution of 4-(N,N-dimethylamino)pyridine (2.9 mg) and N,N-diisopropyl-N-ethylamine (0.0498 ml) in methylene chloride (0.448 ml) and then a solution of trifluoromethanesulfonic anhydride (0.0422 ml) in methylene chloride (0.38 ml) were added thereto at -30° C. After stirring for 30 minutes at the same temperature a solution of N,N-diisopropyl-N-ethylamine (0.833 ml) in methylene chloride (7.497 ml) and a solution of pyridine-4-thiol (159.5 mg) in N,N-dimethylformamide (5.63 ml) were added successively thereto at -30° C. The resultant solution was stirred for 30 minutes at the same temperature and for additional 30 minutes at 0° C. The solvent was distilled off and the residue was dissolved in ethyl acetate, washed twice with water and a saturated aqueous sodium chloride. After drying over magnesium sulfate, the solution was filtered and evaporated. The residue was chromatographed on deactivated silica gel with 10% water (13.5 g), eluting with a mixture of benzene and acetone (100:1 to 6:1) to give 4-nitrobenzyl (5R, 6R)-6-(1-methoxy-1-methylethyl)-7-oxo-3-(4-pyridylthio)-1-azabicyclo[3.2.0]-hept-2-ene-2-carboxylate (379 mg) as a pale yellow solid.

Workup

  1. customat -30° C
  2. customat -30° C
  3. distillationThe solvent was distilled off
  4. dissolutionthe residue was dissolved in ethyl acetate
  5. washwashed twice with water
  6. dry with materialAfter drying over magnesium sulfate
  7. filtrationthe solution was filtered
  8. customevaporated
  9. customThe residue was chromatographed on deactivated silica gel with 10% water (13.5 g)
  10. washeluting with a mixture of benzene and acetone (100:1 to 6:1)

Sources & evidence

ORD record
ord-53d1c65ead214ce3a1813a49f9534209
Source dataset
uspto-grants-1987_02
Patent number
US04640915

Reaction notes

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