Dimethylformamide → 3-[(1RS,2RS,4SR)-4-Bicyclo[2.2.1]-hept-2-yl-phenyl]-5-methoxymethyl-oxazolidin-2-one

HRID 1900050Notes

Reaction equation

HRID 1900050 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH2:12][CH:11]([CH2:13][O:14][CH3:15])[O:10][C:9]2=[O:16])=[CH:4][CH:3]=1.[CH:17]12[CH2:23][CH:20]([CH2:21][CH2:22]1)[CH:19]=[CH:18]2.N1CCCCC1.CN(C)C=O>C(OCC)(=O)C.CC(O)=O.CC(O)=O.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd].C(O)=O>[CH:17]12[CH2:23][CH:20]([CH2:21][CH2:22]1)[CH2:19][CH:18]2[C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH2:12][CH:11]([CH2:13][O:14][CH3:15])[O:10][C:9]2=[O:16])=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 8082PiperidineHCID 103522-NorborneneHCID 22636831(RS)-3-(4-iodophenyl)-5-methoxymethyl-oxazolidin-2-one

Product 1

HCID 700506373-[(1RS,2RS,4SR)-4-Bicyclo[2.2.1]-hept-2-yl-phenyl]-5-methoxymethyl-oxazolidin-2-one

Reagents, catalysts & solvents 3

HCID 10865532Bis(triphenylphosphine)palladium(II) diacetateCatalystHCID 284Formic AcidSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 56 mg of bis-(triphenylphosphine)-palladium (II) diacetate, 0.5 g of (RS)-3-(4-iodophenyl)-5-methoxymethyl-oxazolidin-2-one, 0.16 g of bicyclo[2.2.1]hept-2-ene, 0.5 ml of piperidine, 1 ml of dimethylformamide and 0.15 ml of formic acid was stirred for 3 hours under an argon atmosphere. The reaction mixture was diluted with 50 ml of ethyl acetate and the separated precipitate was removed. The filtrate was extracted twice with 20 ml of water each time, the organic phase was dried over magnesium sulfate and the solvent was distilled off. The brown oil obtained was chromatographed on a 30-fold amount of silica gel with ethyl acetate/hexane (7:3), with 0.43 g of uniform product being obtained after crystallization in ethyl acetate/hexane while cooling. The racemic (1:1) diastereomer mixture melted at 83°-84°.

Workup

  1. customthe separated precipitate was removed
  2. extractionThe filtrate was extracted twice with 20 ml of water each time
  3. dry with materialthe organic phase was dried over magnesium sulfate
  4. distillationthe solvent was distilled off
  5. customThe brown oil obtained
  6. customwas chromatographed on a 30-fold amount of silica gel with ethyl acetate/hexane (7:3), with 0.43 g of uniform product
  7. custombeing obtained
  8. customafter crystallization in ethyl acetate/hexane
  9. temperaturewhile cooling

Sources & evidence

ORD record
ord-edeac957a11f46438998f5309f817f20
Source dataset
uspto-grants-1996_11
Patent number
US05574055

Reaction notes

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