Tetrahydrofuran → HCID 89648652, compound

HRID 1774010Notes

Reaction equation

HRID 1774010 reaction equation
[H-].[Na+].P(=O)([O-])O[C:5]([CH3:17])(C)[C:6]([O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:7].[C:20]([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][N:24]=1)(=O)[CH3:21].[CH2:29]1COCC1>>[CH2:9]([O:8][C:6](=[O:7])/[CH:5]=[C:17](/[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][N:24]=1)\[CH3:29])[C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1.[CH2:9]([O:8][C:6](=[O:7])/[CH:21]=[C:20](\[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][N:24]=1)/[CH3:29])[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 142862-AcetylpyridineHCID 24758Sodium hydrideHCID 178460563HCID 178460563, compound

Product 2

HCID 89648652HCID 89648652, compoundHCID 89648653HCID 89648653, compound

Conditions

Temperature
0 °C

Procedure

To a suspension of sodium hydride 60% dispersion in mineral oil (480 mg, 12 mmol, 1.2 eq.) in THF (20 mL) at 0° C., dimethyl(benzyloxycarbonyl)methyl phosphonate (2.14 ml, 10 mmol, 1.0 eq.) was added dropwise. The mixture was stirred at 0° C. for 15 min. 2-Acetyl pyridine (1.14 mL, 10 mmol, 1.0 eq.) was added dropwise. The mixture was slowly warmed up to r.t. and stirred at r.t. for 18 hours (the ice bath was let expire). The reaction mixture was quenched with sat. aq. NaHCO3 soln. (50 mL). The mixture was extracted with DCM (3×50 mL). The comb. org. phases were washed with sat. aq. NaCl soln., dried over MgSO4, and concentrated in vacuo. The residue was purified by flashmaster (column: 100 g, flow: 45 mL/min, 40 fractions of 45 mL, Heptane 100% to Heptane+40% AcOEt) to yield (E)-3-pyridin-2-yl-but-2-enoic acid benzyl ester as a white solid (LC-MS 3: tR=0.84 min; 254.3) and (Z)-3-pyridin-2-yl-but-2-enoic acid benzyl ester (LC-MS 3: tR=0.63 min; 254.3) as a colorless oil (E/Z ratio ca. 55:13).

Workup

  1. temperatureThe mixture was slowly warmed up to r.t.
  2. customThe reaction mixture was quenched with sat. aq. NaHCO3 soln
  3. extractionThe mixture was extracted with DCM (3×50 mL)
  4. washphases were washed with sat. aq. NaCl soln
  5. dry with material, dried over MgSO4
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flashmaster (column: 100 g, flow: 45 mL/min, 40 fractions of 45 mL, Heptane 100% to Heptane+40% AcOEt)

Sources & evidence

ORD record
ord-18f0a7428bb84da7ae93dbe3eeaeb6a4
Source dataset
uspto-grants-2016_02
Patent number
US09255090B2

Reaction notes

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