Hydrochloric Acid → HCID 67092976, compound

HRID 1261847Notes

Reaction equation

HRID 1261847 reaction equation
Cl([O-])=O.[Na+].[CH2:5]([O:12][C:13]([N:15]1[C@@H:20]([CH3:21])[C:19](=[O:22])[N:18]2[C@@H:23]([CH2:26][CH2:27][OH:28])[CH2:24][O:25][CH:17]2[CH2:16]1)=[O:14])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.S([O-])([O-])(=[O:31])=S.[Na+].[Na+].Cl>P([O-])([O-])([O-])=O.[K+].[K+].[K+].C(#N)C.O.CCOC(C)=O.Cl[O-].[Na+].CC1(C)N([O])C(C)(C)CCC1>[CH2:5]([O:12][C:13]([N:15]1[C@@H:20]([CH3:21])[C:19](=[O:22])[N:18]2[C@@H:23]([CH2:26][C:27]([OH:31])=[O:28])[CH2:24][O:25][CH:17]2[CH2:16]1)=[O:14])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

11

Reactant 4

HCID 313Hydrochloric AcidHCID 24477Sodium ThiosulfateHCID 23668197Sodium ChloriteHCID 67092903HCID 67092903, compound

Product 1

HCID 67092976HCID 67092976, compoundYield 82%

Reagents, catalysts & solvents 6

HCID 2724126TempoCatalystHCID 23665760Sodium HypochloriteCatalystHCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolventHCID 62657Potassium Phosphate, TribasicSolvent

Conditions

Temperature
45 °C

Procedure

Solutions of sodium chlorite (66 mg, 0.58 mmol in 0.5 mL water) and 10% aq. sodium hypochlorite (4 μL, 6 μmol in 0.2 mL water) were added simultaneously at 35° C. to a mixture of (3S,6S)-3-(2-hydroxy-ethyl)-6-methyl-5-oxo-hexahydro-oxazolo[3,2-a]pyrazine-7-carboxylic acid benzyl ester (98 mg, 0.29 mmol), 2,2,6,6-tetramethylpiperidine-1-oxyl radical (3 mg, 20 μmol) in 1 M aq. potassium phosphate buffer (pH 6.85; 0.75 mL) and acetonitrile (1 mL). The reaction mixture was heated at 45° C. for 16 h, then cooled to 0° C., diluted with water and EtOAc and treated with 1 M sodium thiosulfate solution. The pH was then set to 3-4 by addition of 2 M aq. hydrochloric acid solution. The organic layer was washed with brine, dried over magnesium sulfate, filtered, and evaporated. Chromatography (SiO2; DCM→DCM/MeOH/25% aq. ammonia solution 90:10:0.25) afforded the title compound (84 mg, 82%). Colourless gum, MS: 347.1 (M−H)−.

Workup

  1. temperaturecooled to 0° C.
  2. washThe organic layer was washed with brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. customevaporated

Sources & evidence

ORD record
ord-e9bff41b05cc43a6ba282730461cd09d
Source dataset
uspto-grants-2013_06
Patent number
US08471004B2

Reaction notes

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