Hydrogen Peroxide → (6S,8R)-3-(allyl-benzyloxycarbonyl-amino)-8-azido-8-methyl-4-oxo-4,6,7,8-tetrahydro-pyrrolo[1,2-a]pyrimidine-6-carboxylic Acid

HRID 10970

Reaction equation

[CH2:1]([O:8][C:9](=[O:44])[N:10]([CH2:41][CH:42]=[CH2:43])[C:11]1[C:16](=O)[N:15]2[C@H:18]([C:25](N(C(OC(C)(C)C)=O)C3C=CC=CC=3)=[O:26])[CH2:19][C@:20]([N:22]=[N+:23]=[N-:24])([CH3:21])[C:14]2=[N:13][CH:12]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.OO.[Li+].[OH-:48].[O-:49]S([O-])=O.[Na+].[Na+]>C1COCC1.O>[CH2:41]([N:10]([C:9]([O:8][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)=[O:44])[C:11]1[C:16](=[O:48])[N:15]2[C@H:18]([C:25]([OH:49])=[O:26])[CH2:19][C@:20]([N:22]=[N+:23]=[N-:24])([CH3:21])[C:14]2=[N:13][CH:12]=1)[CH:42]=[CH2:43]

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of 18e (480 mg, 0.800 mmol) in 10 mL THF/H2O (4:1) at 0° C., was added 30% H2O2 (1.28 mL, 11.3 mmol) and IN LiOH (1.28 mL, 1.28 mmol). The mixture was stirred at 0° C. of 45 min, then Na2SO3 (1.51 g, 12 mmol) was added. The mixture was stirred 30 min, then evaporated in vacuo. The residue was diluted with Et2O and extracted with 0.1 N NaOH (3×). The combined aqueous was acidified to pH 3 with conc. HCl, then was extracted with EtOAc (5×). The combined organic extract was washed with brine, dried (Na2SO4) and concentrated to afford 272 mg (80%) of a acid 18f, which was used in the following step with out further purification. MS (ESI) 447.3 (M+Na+), 423.2 (M−H+).

Workup

stirringThe mixture was stirred 30 min
customevaporated in vacuo
additionThe residue was diluted with Et2O
extractionextracted with 0.1 N NaOH (3×)
extractionwas extracted with EtOAc (5×)
extractionThe combined organic extract
washwas washed with brine
dry with materialdried (Na2SO4)
concentrationconcentrated

Sources & evidence

ORD record: ord-4dd172fdc643473ca0eacc165e9de0d6
Source dataset: uspto-grants-2006_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07094783B2

Linked notes

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