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Ammonium formate → 1-{(2S,4R)-1-allyloxy-carbonyl-4-(t-butyldimethylsilyloxy) pyrrolidin-2-yl}-1-(1-methylpyrazol-4-yl) methanol

HRID 975670
Notes
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Reaction equation

HRID 975670 reaction equation
C([N:8]1[CH2:12][C@H:11]([O:13][Si:14]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15])[CH2:10][C@H:9]1[CH:21]([C:23]1[CH:24]=[N:25][N:26]([CH3:28])[CH:27]=1)[OH:22])C1C=CC=CC=1.[CH:29]([O-:31])=O.[NH4+]>CO.[Pd]>[CH2:11]([O:13][N:8]1[CH2:12][C@H:11]([O:13][Si:14]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15])[C:10](=[C:29]=[O:31])[C@H:9]1[CH:21]([C:23]1[CH:24]=[N:25][N:26]([CH3:28])[CH:27]=1)[OH:22])[CH:10]=[CH2:9]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 2

HCID 2723923Ammonium formateHCID 54269984(2S,4R)-1-{1-benzyl-4-(t-butyl-dimethylsilyloxy) pyrrolidin-2-yl}-1-(1-methyl-4-pyrazolyl)methanol

Product 1

HCID 867504581-{(2S,4R)-1-allyloxy-carbonyl-4-(t-butyldimethylsilyloxy) pyrrolidin-2-yl}-1-(1-methylpyrazol-4-yl) methanolYield 193%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalyst
HCID 887
Methanol
Solvent

Procedure

To a solution of (2S,4R)-1-{1-benzyl-4-(t-butyl-dimethylsilyloxy) pyrrolidin-2-yl}-1-(1-methyl-4-pyrazolyl)methanol (70 g) in methanol (700 ml) was added ammonium formate (44 g) and 10% Pd-C (wet, 20 g). The mixture was refluxed for 40 minutes, then cooled. After filtration of Pd-C, the solvent was evaporated. To the residue was added chloroform (500 ml) and precipitated excess ammonium formate was filtered off with celite. The filtrate was concentrated under reduced pressure. The residue was dissolved in tetrahydrofuran-water (1:1, 1 l) and a solution of allyl chloroformate (22.3 ml) in tetrahydrofuran (60 ml) was added thereto, while adjusting pH to 8.5~10 with 4N-sodium hydroxide solution at 0°~5° C. The mixture was stirred for 30 minutes at the same temperature. The organic layer was separated and the aqueous layer was extracted with ethyl acetate (×2). The combined organic layer was washed with water and brine, dried over magnesium sulfate and evaporated under reduced pressure to give 1-{(2S,4R)-1-allyloxy-carbonyl-4-(t-butyldimethylsilyloxy) pyrrolidin-2-yl}-1-(1-methylpyrazol-4-yl) methanol (66.2 g).

Workup

  1. temperatureThe mixture was refluxed for 40 minutes
  2. temperaturecooled
  3. filtrationAfter filtration of Pd-C
  4. customthe solvent was evaporated
  5. additionTo the residue was added chloroform (500 ml)
  6. customprecipitated excess ammonium formate
  7. filtrationwas filtered off with celite
  8. concentrationThe filtrate was concentrated under reduced pressure
  9. dissolutionThe residue was dissolved in tetrahydrofuran-water (1:1, 1 l)
  10. additiona solution of allyl chloroformate (22.3 ml) in tetrahydrofuran (60 ml) was added
  11. customat 0°~5° C
  12. customThe organic layer was separated
  13. extractionthe aqueous layer was extracted with ethyl acetate (×2)
  14. washThe combined organic layer was washed with water and brine
  15. dry with materialdried over magnesium sulfate
  16. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-4c9210e79b6545ce8c877436156f8a0e
Source dataset
uspto-grants-1997_03
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05608056

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes