Ethyl Acetate → HCID 11440041, compound

HRID 1243211Notes

Reaction equation

HRID 1243211 reaction equation
C([O:3][C:4]([C:6]1[C:7]([NH:14][C@H:15]2[CH2:19][CH2:18][C@H:17]([O:20][Si:21]([C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:23])[CH3:22])[CH2:16]2)=[N:8][C:9]([S:12][CH3:13])=[N:10][CH:11]=1)=O)C.[H-].[Al+3].[Li+].[H-].[H-].[H-].C(OCC)(=O)C.C(C(C(C([O-])=O)O)O)([O-])=O.[Na+].[K+]>O1CCCC1.[O-2].[O-2].[Mn+4]>[C:24]([Si:21]([CH3:23])([CH3:22])[O:20][C@H:17]1[CH2:18][CH2:19][C@H:15]([NH:14][C:7]2[C:6]([CH:4]=[O:3])=[CH:11][N:10]=[C:9]([S:12][CH3:13])[N:8]=2)[CH2:16]1)([CH3:27])([CH3:26])[CH3:25]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 9855836Potassium sodium tartarateHCID 11338879(-)-(1S,3S)-4-[3-(tert-butyl-dimethyl-silanyloxy)-cyclopentylamino]-2-methylsulfanyl-pyrimidine-5-carboxylic acid ethyl esterHCID 21226445Aluminium lithium hydride

Product 1

HCID 11440041HCID 11440041, compound

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (−)-(1S,3S)-4-[3-(tert-butyl-dimethyl-silanyloxy)-cyclopentylamino]-2-methylsulfanyl-pyrimidine-5-carboxylic acid ethyl ester (910 mg, 2.21 mmol) (from Example 29d supra) in tetrahydrofuran (55 mL) at 0° C. was added in portions lithium aluminum hydride (250 mg, 6.63 mmol) (Aldrich). The reaction mixture was allowed to slowly warm up to room temperature. After stirring overnight the reaction mixture was poured in portions into a vigorously stirred mixture of ethyl acetate and saturated aqueous potassium sodium tartrate solution. The organic layer was collected, dried over sodium sulfate, filtered and concentrated to a solid that was then dissolved in dichloromethane (55 mL). To this solution was added manganese dioxide (1.92 g, 22.11 mmol) (Aldrich) and the mixture was stirred overnight. The slurry was filtered, the solids were washed with tetrahydrofuran (approximately 25 mL) and the combined organic layer was evaporated to a residue that was purified by chromatography on a silica gel column with a 0–50% diethyl ether in hexanes gradient to give (−)-(1S,3S)-4-[3-(tert-butyl-dimethyl-silanyloxy)-cyclopentylamino]-2-methylsulfanyl-pyrimidine-5-carbaldehyde as a viscous colorless oil. (Yield 615 mg, 76%).

Workup

  1. customThe organic layer was collected
  2. dry with materialdried over sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated to a solid
  5. dissolutionthat was then dissolved in dichloromethane (55 mL)
  6. stirringthe mixture was stirred overnight
  7. filtrationThe slurry was filtered
  8. washthe solids were washed with tetrahydrofuran (approximately 25 mL)
  9. customthe combined organic layer was evaporated to a residue that
  10. customwas purified by chromatography on a silica gel column with a 0–50% diethyl ether in hexanes gradient

Sources & evidence

ORD record
ord-946a8ead99904039acc7d1b38bdf6fa4
Source dataset
uspto-grants-2006_10
Patent number
US07115740B2

Reaction notes

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