Sodium Thiosulfate → HCID 58981749, compound

HRID 1182316Notes

Reaction equation

HRID 1182316 reaction equation
[OH:1][C@H:2]([CH2:25][NH:26][S:27]([C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][N:31]=1)(=[O:29])=[O:28])[CH2:3][NH:4][C:5](=[O:24])[O:6][C@H:7]([CH2:12][N:13]1[C:17]2[CH:18]=[C:19]([Cl:23])[C:20]([Cl:22])=[CH:21][C:16]=2[N:15]=[CH:14]1)[C:8]([CH3:11])([CH3:10])[CH3:9].O[C@@H](CNS(C1C=CC=CN=1)(=O)=O)CNC(=O)O[C@H](CN1C2C=C(Cl)C(Cl)=CC=2N=C1)C(C)(C)C.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.S([O-])([O-])(=O)=S.[Na+].[Na+].C(=O)(O)[O-].[Na+]>C(Cl)(Cl)Cl.C(OCC)(=O)C>[O:1]=[C:2]([CH2:25][NH:26][S:27]([C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][N:31]=1)(=[O:29])=[O:28])[CH2:3][NH:4][C:5](=[O:24])[O:6][C@H:7]([CH2:12][N:13]1[C:17]2[CH:18]=[C:19]([Cl:23])[C:20]([Cl:22])=[CH:21][C:16]=2[N:15]=[CH:14]1)[C:8]([CH3:10])([CH3:9])[CH3:11]

Participants

8

Reactant 5

HCID 24477Sodium ThiosulfateHCID 159087Triacetoxyperiodinane2×HCID 516892Sodium BicarbonateHCID 58981701HCID 58981701, compoundHCID 71156681HCID 71156681, compound

Product 1

HCID 58981749HCID 58981749, compoundYield 9.3%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 43 mg (0.079 mmol) of (1S)-1-[(5,6-dichloro-1H-benzimidazol-1-yl)methyl]-2,2-dimethylpropyl (2S)-2-hydroxy-3-[(2-pyridinylsulfonyl)amino]propylcarbamate & (1S)-1-[(5,6-dichloro-1H-benzimidazol-1-yl)methyl]-2,2-dimethylpropyl (2R)-2-hydroxy-3-[(2-pyridinylsulfonyl)amino]propylcarbamate in 2 mL of chloroform was added 42 mg (0.1 mmol) of Dess-Martin periodinane, and the mixture was stirred at room temperature for 1.25 h. An additional portion of 21 mg (0.05 mmol) of Dess-Martin periodinane was added, and the reaction mixture was stirred for another 0.5 h. The mixture was diluted with ethyl acetate and a saturated aqueous sodium thiosulfate solution. The combined layers were mixed vigorously and then a saturated aqueous sodium bicarbonate solution was added. The layers were separated and the organic phase was dried over anhydrous magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography eluting with a methanol:chloroform solution (1:9). The sample was further purified by HPLC using a Waters Symmetry C18 19 mm×150 mm column with 7 μm packing eluted with a five minute gradient of 30%–70% acetonitrile in water. The mobile phase contained a 0.1% trifluoroacetic acid modifier. This purification yielded 4 mg (9%) of (1S)-1-[(5,6-dichloro-1H-benzimidazol-1-yl)methyl]-2,2-dimethylpropyl 2oxo-3-[(2-pyridinylsulfonyl)amino]propylcarbamate. ES-LCMS m/z 542 (M+H) retention time=3.59 min. HRMS C22H25Cl2N5O5S m/z 542.1032 (M+H)Cal; 542.1026 (M+H)Obs.

Workup

  1. stirringthe reaction mixture was stirred for another 0.5 h
  2. additionThe combined layers were mixed vigorously
  3. customThe layers were separated
  4. dry with materialthe organic phase was dried over anhydrous magnesium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified by silica gel column chromatography
  7. washeluting with a methanol
  8. customThe sample was further purified by HPLC
  9. wash19 mm×150 mm column with 7 μm packing eluted with a five minute gradient of 30%–70% acetonitrile in water
  10. customThis purification

Sources & evidence

ORD record
ord-d28e1cdd3a5c4613a99c2c1f8ed7c7ba
Source dataset
uspto-grants-2007_10
Patent number
US07288541B2

Reaction notes

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