Sodium Carbonate → (3R)-3-(triethylsilyloxy)-4-methyl-5-(2-methylthiazol-4-yl)-pent-4-enal

HRID 1357394Notes

Reaction equation

HRID 1357394 reaction equation
[CH2:1]([Si:3]([CH2:20][CH3:21])([CH2:18][CH3:19])[O:4][C@@H:5]([C:9]([CH3:17])=[CH:10][C:11]1[N:12]=[C:13]([CH3:16])[S:14][CH:15]=1)[CH2:6][CH:7]=C)[CH3:2].C[N+]1([O-])CC[O:26]CC1.[O-]S([O-])=O.[Na+].[Na+].C([O-])(=O)C.C([O-])(=O)C.C([O-])(=O)C.C([O-])(=O)C.[Pb+4].C([O-])([O-])=O.[Na+].[Na+]>C(O)(C)(C)C.C1C=CC=CC=1.[Os](=O)(=O)(=O)=O.O>[CH2:1]([Si:3]([CH2:20][CH3:21])([CH2:18][CH3:19])[O:4][C@@H:5]([C:9]([CH3:17])=[CH:10][C:11]1[N:12]=[C:13]([CH3:16])[S:14][CH:15]=1)[CH2:6][CH:7]=[O:26])[CH3:2]

Participants

10

Reactant 5

HCID 10340Sodium CarbonateHCID 24437Sodium SulfiteHCID 82029Methyl morpholine oxideHCID 69507819(4R)-4-(triethylsilyloxy)-5-methyl-6-(2-methylthiazol-4-yl)-1,5-hexadieneHCID 178418268HCID 178418268, compound

Product 1

HCID 86586609(3R)-3-(triethylsilyloxy)-4-methyl-5-(2-methylthiazol-4-yl)-pent-4-enal

Reagents, catalysts & solvents 4

HCID 30318Osmium TetroxideCatalystHCID 241BenzeneSolventHCID 962WaterSolvent2×HCID 6386tert-ButanolSolvent

Procedure

Osmium tetraoxide (1 wt % in THF, 20.3 mL) is added to a mixture of (4R)-4-(triethylsilyloxy)-5-methyl-6-(2-methylthiazol-4-yl)-1,5-hexadiene (13.5 g), H2O (21 mL), and N-methylmorpholine N-oxide (50% in THF, 10 mL, 0.048 mol) in tert-butanol (155 mL) at 0° C. After the resulting mixture is stirred for 12 hours, Na2SO3 (10 g) and water (5 mL) are added. The resulting solution is stirred at 25° C. for 30 minutes and then extracted with ether. The combined extracts are washed with brine, dried (Na2SO4), filtered, and concentrated. Purification by flash chromatography on SiO2 provides a 1:1 diastereomeric mixture of the diol as a colorless, viscous oil. Lead tetraacetate (19.1 g) is added portionwise over 5 minutes to a suspension of the diol (18.0 g) and Na2CO3 (8.67 g) in 500 mL of benzene at 0° C. After stirring for 15 minutes, the mixture is filtered through a SiO2 pad to afford the aldehyde product. The product is directly subjected to the next reaction.

Workup

  1. stirringThe resulting solution is stirred at 25° C. for 30 minutes
  2. extractionextracted with ether
  3. washThe combined extracts are washed with brine
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customPurification by flash chromatography on SiO2
  8. customprovides
  9. stirringAfter stirring for 15 minutes
  10. filtrationthe mixture is filtered through a SiO2 pad

Sources & evidence

ORD record
ord-a3849978025a46cfa1430f84f78f9988
Source dataset
uspto-grants-2003_07
Patent number
US06589968B2

Reaction notes

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