Ammonium Chloride → cis-Ethyl 4-hydroxy-2-methylcyclopent-2-enecarboxylate

HRID 2204521노트

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HRID 2204521 반응식
[CH3:1][C:2]1[CH:3]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:4][C:5](=[O:7])[CH:6]=1.O.O.O.O.O.O.O.[Cl-].[Ce+3].[Cl-].[Cl-].[BH4-].[Na+].[NH4+].[Cl-]>CCOCC.CO>[OH:7][C@@H:5]1[CH2:4][C@H:3]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:2]([CH3:1])=[CH:6]1

참가 물질

7

반응물 4

HCID 25517Ammonium ChlorideHCID 4311764Sodium borohydrideHCID 11332690Ethyl 2-methyl-4-oxocyclopent-2-ene-1-carboxylateHCID 21585214Cerium trichloride heptahydrate

생성물 1

HCID 10877556cis-Ethyl 4-hydroxy-2-methylcyclopent-2-enecarboxylate수율 46.6%

시약·촉매·용매 2

HCID 887Methanol용매HCID 3283Diethyl Ether용매

실험 절차

A round-bottom flask was charged with ethyl 2-methyl-4-oxocyclopent-2-enecarboxylate (2.04 g, 12.1 mmol, Preparation #CC.1), MeOH (30 mL), and cerium(III) chloride heptahydrate (5.65 g, 15.2 mmol) followed by portion-wise addition of sodium borohydride (0.574 g, 15.2 mmol). The suspension was stirred at room temperature over about 16 h. Saturated aqueous NH4Cl solution (50 mL) was added. The mixture was stirred for about 10 min and Et2O (60 mL) was added. The layers were separated and the aqueous layer was extracted with Et2O (3×30 mL). The combined organic layers were washed with saturated aqueous NaHCO3, dried over anhydrous MgSO4, filtered, and concentrated to dryness under reduced pressure. The residue was purified via silica gel chromatography eluting with 20-60% EtOAc/pentane to yield cis-ethyl 4-hydroxy-2-methylcyclopent-2-enecarboxylate (0.96 g, 46%): 1H NMR (400 MHz, CDCl3) δ 5.77-5.71 (m, 1H), 4.63 (m, 1H), 4.28-4.11 (m, 2H), 3.27-3.20 (m, 1H), 2.59 (bs, 1H), 2.41-2.30 (m, 1H), 2.00 (d, J=14.2 Hz, 1H), 1.79 (d, =1.2 Hz, 3H), 1.30 (t, J=7.1 Hz, 3H) and trans-ethyl 4-hydroxy-2-methylcyclopent-2-enecarboxylate (0.69 g, 33%): 1H NMR (400 MHz, CDCl3) δ 5.63 (dd, J=1.8, 3.4 Hz, 1H), 4.98 (m, 1H), 4.20-4.11 (m, 2H), 3.60-3.53 (m, 1H), 2.57 (ddd, J=4.4, 7.1, 13.9 Hz, 1H), 1.98 (ddd, J=3.5, 8.4, 13.9 Hz, 1H), 1.80 (d, J=1.4, 3H), 1.46 (bs, 1H), 1.27 (t, J=7.1 Hz, 3H).

후처리

  1. stirringThe mixture was stirred for about 10 min
  2. customThe layers were separated
  3. extractionthe aqueous layer was extracted with Et2O (3×30 mL)
  4. washThe combined organic layers were washed with saturated aqueous NaHCO3
  5. dry with materialdried over anhydrous MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated to dryness under reduced pressure
  8. customThe residue was purified via silica gel chromatography
  9. washeluting with 20-60% EtOAc/pentane

출처 및 근거

ORD 기록
ord-abc3039d7b7d47cf9542e3dbbc19f2a0
출처 데이터셋
uspto-grants-2016_06
특허 번호
US09365579B2

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