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Hydrochloric Acid → (3S,4S)-1-Benzyloxycarbonyl-3-(tert-butoxycarbonyl)amino-4-vinylpyrrolidine

HRID 1253422
Notes
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Reaction equation

HRID 1253422 reaction equation
ICI.[CH2:4]([O:11][C:12]([N:14]1[CH2:18][C@H:17]([CH:19]=O)[C@H:16]([NH:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:15]1)=[O:13])[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.Cl.[CH2:30](OCC)C>O1CCCC1.[Ti](Cl)(Cl)(Cl)Cl.[Zn]>[CH2:4]([O:11][C:12]([N:14]1[CH2:18][C@H:17]([CH:19]=[CH2:30])[C@H:16]([NH:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:15]1)=[O:13])[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 3283Diethyl EtherHCID 6346DiiodomethaneHCID 59665257(3S,4S)-1-Benzyloxycarbonyl-3-(tert-butoxycarbonyl)amino-4-formylpyrrolidine

Product 1

HCID 59665269(3S,4S)-1-Benzyloxycarbonyl-3-(tert-butoxycarbonyl)amino-4-vinylpyrrolidine

Reagents, catalysts & solvents 3

HCID 23994
Zinc
Catalyst
HCID 24193Titanium TetrachlorideCatalyst
HCID 8028TetrahydrofuranSolvent3×

Procedure

Under cooling with ice, titanium tetrachloride (3.30 mL, 1.0M toluene solution) was added to a suspension of zinc powder (1.86 g, 28.5 mmol) in tetrahydrofuran (15 mL) over 2 minutes, followed by stirring for 5 minutes at the same temperature. A solution of diiodomethane (1.15 mL, 14.3 mL) in tetrahydrofuran (5 mL) was added thereto over 8 minutes, and the resultant mixture was stirred for 15 minutes while the temperature thereof was elevated to room temperature. A solution of (3S,4S)-1-benzyloxycarbonyl-3-(tert-butoxycarbonyl)amino-4-formylpyrrolidine (900 mg, 2.58 mmol) in tetrahydrofuran (5.0 mL) was added thereto over 7 minutes, followed by stirring for 1.5 hours. Subsequently, under cooling with ice, the resultant mixture was poured to 0.5 mol/L hydrochloric acid (10 mL), followed by dilution with diethyl ether (60 mL). The obtained aqueous layer was extracted with diethyl ether (100 mL×2). The combined organic layer was washed by saturated brine (100 mL), dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure. The obtained residue was purified through silica gel column chromatography (ethyl acetate:n-hexane=1:3), to thereby yield the title compound as a colorless oily substance (3.09 g, 31%).

Workup

  1. waitover 8 minutes
  2. customthereof was elevated to room temperature
  3. waitover 7 minutes
  4. stirringby stirring for 1.5 hours
  5. temperatureSubsequently, under cooling with ice
  6. extractionThe obtained aqueous layer was extracted with diethyl ether (100 mL×2)
  7. washThe combined organic layer was washed by saturated brine (100 mL)
  8. dry with materialdried over anhydrous sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customThe obtained residue was purified through silica gel column chromatography (ethyl acetate:n-hexane=1:3)

Sources & evidence

ORD record
ord-a4576d6391794d649ef42d25612fb0c8
Source dataset
uspto-grants-2013_06
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08455482B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes