Methanol → HCID 70245767, compound

HRID 1976231Notes

Reaction equation

HRID 1976231 reaction equation
CO[C:3](=O)[C@@H:4]1[CH2:8][C@@H:7]([O:9][Si:10]([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11])[CH2:6][N:5]1[C:17](=[O:27])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[N+:24]([O-])=O.[H-].C([Al+]CC(C)C)C(C)C.CO.[Cl-].[NH4+]>ClCCl>[Si:10]([O:9][C@H:7]1[CH2:6][N:5]2[C@H:4]([CH2:3][NH:24][C:19]3[CH:20]=[CH:21][CH:22]=[CH:23][C:18]=3[C:17]2=[O:27])[CH2:8]1)([C:13]([CH3:14])([CH3:16])[CH3:15])([CH3:11])[CH3:12]

Participants

6

Reactant 4

HCID 887MethanolHCID 25517Ammonium ChlorideHCID 21225700DiisobutylaluminumhydrideHCID 57019258HCID 57019258, compound

Product 1

HCID 70245767HCID 70245767, compoundYield 51.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-70 °C

Procedure

To a solution of 9.0 g of (2S, 4R)-4-(tert-butyldimethylsilyloxy)-1-(2-nitrobenzoyl) proline methyl ester in 90 ml of dichloromethane, there was dropwise added 44 ml of a 1M solution of diisobutyl aluminum hydride in dichloromethane at −70° C. over 30 minutes in a nitrogen gas atmosphere and then the mixture was stirred at −70° C. for one hour. A mixture containing 1 ml of methanol and 1 ml of dichloromethane was added to the reaction solution at −60° C., then 10 ml of a saturated aqueous ammonium chloride solution was added thereto and the mixture was stirred at room temperature for one hour. The precipitates separated out were filtered off, the filtrate was washed with water, dried and concentrated under reduced pressure. The resulting oily substance was dissolved in 50 ml of methanol, followed by addition of 4.5 g of a 10% palladium-carbon catalyst to the solution and stirring at room temperature for 15 hours in a hydrogen gas atmosphere. The catalyst present in the reaction solution was filtered off and the filtrate was concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography, followed by elution with methanol/chloroform. (1/100) to thus give 3.7 g (yield 51.2%) of the title compound.

Workup

  1. customat −70° C.
  2. customover 30 minutes
  3. additionwas added to the reaction solution at −60° C.
  4. stirringthe mixture was stirred at room temperature for one hour
  5. customThe precipitates separated out
  6. filtrationwere filtered off
  7. washthe filtrate was washed with water
  8. customdried
  9. concentrationconcentrated under reduced pressure
  10. dissolutionThe resulting oily substance was dissolved in 50 ml of methanol
  11. additionfollowed by addition of 4.5 g of a 10% palladium-carbon catalyst to the solution
  12. stirringstirring at room temperature for 15 hours in a hydrogen gas atmosphere
  13. filtrationThe catalyst present in the reaction solution was filtered off
  14. concentrationthe filtrate was concentrated under reduced pressure
  15. washfollowed by elution with methanol/chloroform

Sources & evidence

ORD record
ord-4cc04a2f5d044aaab5b51108665497d4
Source dataset
uspto-grants-2001_05
Patent number
US06225306B1

Reaction notes

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