Water → HCID 18955973, compound

HRID 2379706Notes

Reaction equation

HRID 2379706 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH2:13][S:12][CH:11]2[N:8]([C:9](=[O:16])[C:10]2=[N+]=[N-])[C:7]=1[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])(=[O:3])[CH3:2].[CH2:24](B(CC)CC)[CH3:25].O>C1COCC1>[C:1]([O:4][CH2:5][C:6]1[CH2:13][S:12][CH:11]2[N:8]([C:9](=[O:16])[CH:10]2[CH2:24][CH3:25])[C:7]=1[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 962WaterHCID 7357TriethylboraneHCID 12878654HCID 12878654, compound

Product 1

HCID 18955973HCID 18955973, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
-78 °C

Procedure

A 2 liter, 3-necked round bottom flask fitted with 2 dropping funnels was charged with 200 ml THF and cooled to -78° C. under N2. One dropping funnel was charged with a solution of 6.33 g (15.3 mM] t-butyl 3-acetyloxymethyl-7-diazo-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate in 300 ml THF. The other funnel was charged with 32 ml 1M-triethylborane in THF, 1.2 ml H2O, and 300 ml THF. The funnels were adjusted so their contents were added to the flask at 2.5 ml/min and the temperature of the reaction mixture maintained at -78°. After the addition, the cooling bath was removed and the reaction mixture allowed to warm. When the temperature reached -45° C., 6.67 ml 30% H2O2 was added. At -15°, the reaction mixture was washed with 300 ml brine, the organic layer diluted with 300 ml CH2Cl2, washed with 300 ml brine, dried over MgSO4, filtered and stripped to give 7.46 g of yellow oil which was chromatographed on a flash column with CHCl3 /EtOAc (25:1) to yield 1.289 g (19%) t-butyl-3-acetyl-oxymethyl-7α-ethyl-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate a 4:1 mixture of the α and β isomers. NMR(CDCl3): δ1.08, t (J=8 Hz), 3H; 1.50, s, 9H; 1.8, br, qt, 2H; 2.05, s, 3H; 3.1, brm, 1H; 3.4, d, 2H; 4.35, d (J=2Hz), 1H; 4.82, AB qt (J=12, 6Hz) 2H.

Workup

  1. customA 2 liter, 3-necked round bottom flask fitted with 2 dropping funnels
  2. additionwere added to the flask at 2.5 ml/min
  3. temperaturethe temperature of the reaction mixture maintained at -78°
  4. additionAfter the addition
  5. customthe cooling bath was removed
  6. temperatureto warm
  7. customreached -45° C.
  8. addition6.67 ml 30% H2O2 was added
  9. washAt -15°, the reaction mixture was washed with 300 ml brine
  10. additionthe organic layer diluted with 300 ml CH2Cl2
  11. washwashed with 300 ml brine
  12. dry with materialdried over MgSO4
  13. filtrationfiltered

Sources & evidence

ORD record
ord-3a1182b96a4944228c672a153b134331
Source dataset
uspto-grants-1994_11
Patent number
US05364848

Reaction notes

Loading…