Hydrochloric Acid → (3S,4S)-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4-[(1R)-1-{(phenylthio)thiocarbonyl}ethyl]-2-oxoazetidine

HRID 1464732Notes

Reaction equation

HRID 1464732 reaction equation
C(N(CC)CC)C.C(O[C@H:12]1[NH:15][C:14](=[O:16])[C@@H:13]1[C@H:17]([O:19][Si:20]([C:23]([CH3:26])([CH3:25])[CH3:24])([CH3:22])[CH3:21])[CH3:18])(=O)C.[C:27]([S:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)(=[S:30])[CH2:28][CH3:29].Cl>C(#N)C.[Cl-].[Zn+2].[Cl-].[Cu]Cl.ClCCl>[Si:20]([O:19][C@@H:17]([C@@H:13]1[C@@H:12]([C@H:28]([C:27]([S:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)=[S:30])[CH3:29])[NH:15][C:14]1=[O:16])[CH3:18])([C:23]([CH3:24])([CH3:25])[CH3:26])([CH3:21])[CH3:22]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 10935078AzetidonHCID 13148853Phenyl dithiopropionate

Product 1

HCID 22851409(3S,4S)-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4-[(1R)-1-{(phenylthio)thiocarbonyl}ethyl]-2-oxoazetidineYield 68.4%

Reagents, catalysts & solvents 4

HCID 62652Cuprous chlorideCatalystHCID 3007855ZincchlorideCatalystHCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a suspension of anhydrous zinc chloride (56 mg) in acetonitrile (1.6 ml) cooled to 0° C. was added triethylamine (0.17 ml). After stirring for 10 minutes at 0° C., to the solution were added copper(I) chloride (41 mg), (3R,4R)-4-acetoxy-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-2-oxoazetidine (79 mg) and phenyl dithiopropionate (75 mg). The reaction mixture was stirred at 0° C. for 2 hours. The mixture was poured into a stirred mixture of dichloromethane (5 ml) and 1N aqueous hydrochloric acid solution (5 ml). The organic layer was separated, washed with water, aqueous sodium bicarbonate solution and brine, and dried. The solution was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (ethyl acetate:n-hexane=1:4, V/V) to afford a mixture (5:1) (77 mg) of (3S,4S)-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4-[(1R)-1-{(phenylthio)thiocarbonyl}ethyl]- 2-oxoazetidine and (3S,4S)-3-[(1R)-1-(tert-butyldimethylsilyloxy)ethyl]-4-[(1S)-1-{(phenylthio)thiocarbonyl}ethyl]-2-oxoazetidine.

Workup

  1. stirringThe reaction mixture was stirred at 0° C. for 2 hours
  2. customThe organic layer was separated
  3. washwashed with water, aqueous sodium bicarbonate solution and brine
  4. customdried
  5. concentrationThe solution was concentrated under reduced pressure
  6. customthe residue was purified by silica gel column chromatography (ethyl acetate:n-hexane=1:4, V/V)

Sources & evidence

ORD record
ord-00f2721800bf4c3fa05415a69cadfaf0
Source dataset
uspto-grants-1994_04
Patent number
US05306816

Reaction notes

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