Sodium Bisulfite → HCID 58687952, compound

HRID 746419Notes

Reaction equation

HRID 746419 reaction equation
[CH2:1]([C:4]1[C:5]([O:23][CH3:24])=[N:6][C:7]([C:19]([F:22])([F:21])[F:20])=[CH:8][C:9]=1[CH2:10][O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13])[CH:2]=C.S(=O)(O)[O-:26].[Na+].I([O-])(=O)(=O)=O.[Na+]>CC(C)=O.O.CO.O.[Os](=O)(=O)(=O)=O>[Si:12]([O:11][CH2:10][C:9]1[CH:8]=[C:7]([C:19]([F:21])([F:22])[F:20])[N:6]=[C:5]([O:23][CH3:24])[C:4]=1[CH2:1][CH:2]=[O:26])([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13]

Participants

7

Reactant 3

HCID 23665763Sodium BisulfiteHCID 23667635Sodium periodateHCID 58687967HCID 58687967, compound

Product 1

HCID 58687952HCID 58687952, compoundYield 61.1%

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalystHCID 18366337Propan-2-one--water (1/1)SolventHCID 22242641Methanol--water (1/1)Solvent

Procedure

A mixture of 3-allyl-4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-2-methoxy-6-(trifluoromethyl)pyridine (2.62 g, 7.25 mmol), N-methylmorphine N-oxide (849 mg, 7.25 mmol), osmium tetroxide (4 wt. % in water, 10 mL, 400 mg) in acetone/water (4:1) (100 mL) was stirred at room temperature overnight. The reaction was quenched by sodium bisulfite (3.50 g, 36 mmol). After acetone was evaporated, the mixture was diluted with water, and extracted with DCM. The organic layer was dried over Na2SO4, filtered, and concentrated. The residue was stirred with sodium periodate (1.86 g, 8.7 mmol) in MeOH/water (1:1) (60 mL) for 30 min. The reaction was filtered and concentrated. The residue was partitioned between ethyl acetate and water and the aqueous layer was extracted by ethyl acetate. The combined organic layers were dried over Na2SO4, filtered, and concentrated under vacuum. The residue was purified by column chromatography (silica gel, 30% EtOAc/hexane) to yield [4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-2-methoxy-6-(trifluoromethyl)pyridin-3-yl]acetaldehyde (1.61 g, 61%). 1H-NMR (400 MHz, CDCl3) δ 9.68 (t, J=1.5 Hz, 1H), 7.46 (s, 1H), 4.67 (s, 2H), 4.01 (s, 3H), 3.76 (d, J=5 Hz, 2H), 0.96 (s, 9H), 0.13 (s, 6H).

Workup

  1. customAfter acetone was evaporated
  2. additionthe mixture was diluted with water
  3. extractionextracted with DCM
  4. dry with materialThe organic layer was dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. filtrationThe reaction was filtered
  8. concentrationconcentrated
  9. customThe residue was partitioned between ethyl acetate and water
  10. extractionthe aqueous layer was extracted by ethyl acetate
  11. dry with materialThe combined organic layers were dried over Na2SO4
  12. filtrationfiltered
  13. concentrationconcentrated under vacuum
  14. customThe residue was purified by column chromatography (silica gel, 30% EtOAc/hexane)

Sources & evidence

ORD record
ord-87867dab5334457f88d2522f992fceb9
Source dataset
uspto-grants-2008_07
Patent number
US07393844B2

Reaction notes

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