Tetrahydrofuran → (R*,R*)-alpha-2-propenyloxiraneethanol

HRID 893486

반응식

HRID 893486 반응식
C([Li])CCC.[CH2:6]=[CH:7][CH2:8][CH:9]([OH:13])[CH2:10][CH:11]=[CH2:12].C1(C(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[O:33]1CCCC1>>[CH2:8]([C@@H:9]([OH:13])[CH2:10][C@@H:11]1[CH2:12][O:33]1)[CH:7]=[CH2:6]

참가 물질

5

반응물 4

HCID 8028TetrahydrofuranHCID 10614TriphenylmethaneHCID 17902Hepta-1,6-dien-4-olHCID 178418339Butyllithium

생성물 1

HCID 13895984(R*,R*)-alpha-2-propenyloxiraneethanol

실험 절차

n-Butyllithium, 129 mL (200 mmol), is added dropwise to a 0° C. solution of 1,6-heptadien-4-ol, 22.4 g (0.2 mol), in 200 mL of anhydrous tetrahydrofuran until the triphenylmethane indicator turned red. Carbon dioxide is then bubbled in for 30 minutes (lecture bottle carbon dioxide passed through drierite) and the light yellow solution is stirred for 30 minutes under a balloon of carbon dioxide. To this solution is added iodine, 101.4 g (0.4 mol), dissolved in ~200 mL of anhydrous tetrahydrofuran over 60 minutes. The mixture is allowed to warm to room temperature overnight, diluted with ethyl acetate, washed with 10% sodium bisulfite solution, saturated solution of sodium bicarbonate, brine, and dried (magnesium sulfate). The crude product is dissolved in 200 mL of methanol and 20 mL of water, cooled to 0° C. and 0.5 g of solid potassium carbonate is added. The mixture is vigorously stirred for six hours, filtered, concentrated, and partitioned between ethyl acetate and brine. After extracting the aqueous layer 2x with ethyl acetate, the combined organics are washed with brine and dried (magnesium sulfate). Flash chromatography (4:1 hexane-ethyl acetate) provides, after concentration in vacuo, 18 g of (R*,R*)-α-2-propenyloxiraneethanol. 200 MHz NMR (CDCl3) δ1.5-1.65 (m, 1H), 1.90 (dt, 1H, J=15, 4 Hz), 2.2 (m, 3H), 2.53 (m, 1H), 2.79 (m, 1H), 3.12 (m, 1H), 3.94 (m, 1H), 5.19 (m, 2H), 5.80 (m, 1H).

후처리

  1. customCarbon dioxide is then bubbled in for 30 minutes (lecture bottle carbon dioxide passed through drierite)
  2. additionTo this solution is added iodine, 101.4 g (0.4 mol)
  3. dissolutiondissolved in ~200 mL of anhydrous tetrahydrofuran over 60 minutes
  4. additiondiluted with ethyl acetate
  5. washwashed with 10% sodium bisulfite solution, saturated solution of sodium bicarbonate, brine
  6. dry with materialdried (magnesium sulfate)
  7. dissolutionThe crude product is dissolved in 200 mL of methanol
  8. temperature20 mL of water, cooled to 0° C.
  9. addition0.5 g of solid potassium carbonate is added
  10. stirringThe mixture is vigorously stirred for six hours
  11. filtrationfiltered
  12. concentrationconcentrated
  13. custompartitioned between ethyl acetate and brine
  14. extractionAfter extracting the aqueous layer 2x with ethyl acetate
  15. washthe combined organics are washed with brine
  16. dry with materialdried (magnesium sulfate)
  17. customFlash chromatography (4:1 hexane-ethyl acetate) provides
  18. concentrationafter concentration in vacuo, 18 g of (R*,R*)-α-2-propenyloxiraneethanol

출처 및 근거

ORD 기록
ord-800f0d79e87f46edb16a2343cf5fe5ac
출처 데이터셋
uspto-grants-1992_06
특허 번호
US05124482

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