Ethyl Acetate → (RS)-3-[5-(1,4-dioxa-spiro[4,5]dec-7-en-8-yl)-pyridin-2-yl]-5-methoxymethyl-oxazolidin-2-one

HRID 1900079Notes

Reaction equation

HRID 1900079 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([N:8]2[CH2:12][CH:11]([CH2:13][O:14][CH3:15])[O:10][C:9]2=[O:16])=[N:6][CH:7]=1.C[Sn](C)(C)[C:19]1[CH2:28][CH2:27][C:22]2([O:26][CH2:25][CH2:24][O:23]2)[CH2:21][CH:20]=1.C(OCC)(=O)C.[F-].[K+]>O1CCCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[O:23]1[C:22]2([CH2:27][CH2:28][C:19]([C:2]3[CH:3]=[CH:4][C:5]([N:8]4[CH2:12][CH:11]([CH2:13][O:14][CH3:15])[O:10][C:9]4=[O:16])=[N:6][CH:7]=3)=[CH:20][CH2:21]2)[O:26][CH2:25][CH2:24]1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 522689Potassium FluorideHCID 111741648-Trimethylstannyl-1,4-dioxa-spiro[4,5]dec-7-eneHCID 233718183-(5-Bromo-pyridin-2-yl)-5-methoxymethyl-oxazolidin-2-one

Product 1

HCID 23371891(RS)-3-[5-(1,4-dioxa-spiro[4,5]dec-7-en-8-yl)-pyridin-2-yl]-5-methoxymethyl-oxazolidin-2-oneYield 37.5%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

A suspension of 1.4 g of 3-(5-bromo-pyridin-2-yl)-5-methoxymethyl-oxazolidin-2-one, 1.4 g of 8-trimethylstannyl-1,4-dioxa-spiro[4,5]dec-7-ene and 0.3 of bis(triphenylphosphine)palladium(II) dichloride in 20 ml of tetrahydrofuran was stirred at 70° under argon for 18 h. Then, the mixture was cooled, treated with 150 ml of ethyl acetate and 150 ml of saturated potassium fluoride solution and stirred for 30 minutes. The mixture was filtered over a Celite® pad, the phases were separated and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, dried with magnesium sulfate, concentrated and chromatographed over silica gel 60 with diethyl ether as the eluent. There was obtained 0.6 g of (RS)-3-[5-(1,4-dioxa-spiro[4,5]dec-7-en-8-yl)-pyridin-2-yl]-5-methoxymethyl-oxazolidin-2-one. 1H-nmr(CDCl3) ppm: 8.41 (s, 1H), 8.03 (d, 1H), 7.89 (d, 1H), 6.08 (t, 1H), 4.82 (m, 1H), 4.21 (t, 1H), 3.91 (t, 1H), 3.92 (s, 4H), 3.60 (m, 2H), 3.32 (s, 3H), 2.54 (m, 2H), 2.38 (m, 2H), 1.82 (t, 2H).

Workup

  1. temperatureThen, the mixture was cooled
  2. stirringstirred for 30 minutes
  3. filtrationThe mixture was filtered over a Celite® pad
  4. customthe phases were separated
  5. extractionthe aqueous phase was extracted with ethyl acetate
  6. dry with materialdried with magnesium sulfate
  7. concentrationconcentrated
  8. customchromatographed over silica gel 60 with diethyl ether as the eluent

Sources & evidence

ORD record
ord-3c7be97ab065488eb9327708844e6e30
Source dataset
uspto-grants-1996_11
Patent number
US05574055

Reaction notes

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