Furfural → HCID 22498771, compound

HRID 2307285Notes

Reaction equation

HRID 2307285 reaction equation
[C:1]([N:8]1[CH2:12][CH2:11][CH2:10][CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].CN(C)CCN(C)C.C([Li])(CC)C.[O:26]1[CH:30]=[CH:29][CH:28]=[C:27]1[CH:31]=[O:32]>C(OCC)C>[O:26]1[CH:30]=[CH:29][CH:28]=[C:27]1[CH:31]([CH:12]1[CH2:11][CH2:10][CH2:9][N:8]1[C:1]([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2])[OH:32]

Participants

6

Reactant 4

HCID 7362FurfuralHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 643455N-Boc-pyrrolidineHCID 178418400CID 53628100

Product 1

HCID 22498771HCID 22498771, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

N-Boc-pyrrolidine (5.0 g) is dissolved in diethyl ether (60 mL) and the solution is cooled to −78° C. N,N,N′,N′-Tetramethylethylenediamine (TMEDA) (4.4 mL) is added to the mixture followed by sec-butyl lithium (27.0 mL, 1.3 M in cyclohexane) maintaining the temperature below −60° C. After 2 h, 2-furaldehyde (2.9 mL) is added and the mixture is stirred at −70° C. for an additional 30 min. The reaction mixture is allowed to warm to room temperature and is then quenched with water (25 mL) and poured into EtOAc (200 mL). The separated organic layer is washed with saturated aq. ammonium chloride (3×50 mL) followed by brine (50 mL), dried (MgSO4), and concentrated The crude product is purified by column chromatography (heptane/EtOAc, 8/1; 5/1) to afford 4.97 g of 2-furyl(N-Boc-pyrrolidin-2-yl)methanol as a mixture of diastereomers. The resulting 2-furyl(N-Boc-pyrrolidin-2-yl)methanol (4.43 g) is dissolved in dichloromethane (200 mL) and trifluoroacetic acid (30 mL) is added. The mixture is poured into a 1 M solution of sodium hydroxide. The organic layer is separated and washed with saturated aq. sodium bicarbonate (2×100 mL). The aqueous layers are extracted with dichloromethane (4×50 mL) and the combined organic layers are concentrated. The crude product is purified by column chromatography (CH2Cl2/methanol/NH4OH, 95/5/1; 90/10/1). The resulting oil is distilled in a Kugelrohr apparatus (0.175-200° C., 0.2 Torr) to afford 0.20 g of the title compound as a mixture of diastereomers. Physical characteristics. MS (ESI+) m/z 168 (M+H)+.

Workup

  1. temperaturemaintaining the temperature below −60° C
  2. temperatureto warm to room temperature
  3. customis then quenched with water (25 mL)
  4. additionpoured into EtOAc (200 mL)
  5. washThe separated organic layer is washed with saturated aq. ammonium chloride (3×50 mL)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated The crude product
  8. customis purified by column chromatography (heptane/EtOAc, 8/1; 5/1)

Sources & evidence

ORD record
ord-1db34dd11b0f4efeb8532be3e356855a
Source dataset
uspto-grants-2004_12
Patent number
US06831081B2

Reaction notes

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