Diethyl Ether → HCID 66930888, compound

HRID 511998Notes

Reaction equation

HRID 511998 reaction equation
[CH3:1][N:2]1[NH:6][CH:5]=[CH:4]O1.[Li]CCCC.[Mg+2].[Br-].[Br-].CC[O:17]CC.[O:20]([CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH:33]=[O:34])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>C1COCC1>[O:20]([CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH:33]([C:1]1[O:17][C:5]([CH3:4])=[N:6][N:2]=1)[OH:34])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

7

Reactant 5

HCID 3283Diethyl EtherHCID 82241Magnesium BromideHCID 20213174HCID 20213174, compoundHCID 86636787HCID 86636787, compoundHCID 178418339Butyllithium

Product 1

HCID 66930888HCID 66930888, compoundYield 53.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-50 °C

Procedure

To a stirred solution of 63 (0.252 g, 3 mmol) in anhydrous THF (5 mL), at −78° C., under a nitrogen atmosphere, was added n-BuLi (1.2 mL, 3 mmol, using a 2.5 M solution in hexanes) dropwise. Stirring was continued for 15 min at −78° C. and then MgBr2.Et2O (0.774 g, 3 mmol) was added. The resulting mixture was warmed to −50° C. over a 2 hours period, and then it was transferred by cannula to a cooled (−78° C.) slurry of 62.1 (0.125 g, 0.6 mmol) and CeCl3, (0.738 g, 3 mmol) in anhydrous THF (6 mL), which was previously stirred at room temperature for 2 hours under nitrogen. Following the addition, the resultant mixture was allowed to warm to room temperature over a 4 hours period. The reaction mixture was quenched with dropwise addition of 5% aqueous AcOH solution (10 mL), diluted with AcOEt (20 mL) and the organic phase was separated. The aqueous layer extracted with AcOEt, the combined organic layer was washed with aqueous saturated NaHCO3 solution and brine, dried (MgSO4) and the solvent was evaporated under reduced pressure. The residue obtained was purified by flash column chromatography on silica gel (75% ethyl acetate-hexane) to give 64.1 (92.5 mg, 53% yield) as a white solid (m p 50-52° C.).

Workup

  1. stirringwas previously stirred at room temperature for 2 hours under nitrogen
  2. additionthe addition
  3. temperatureto warm to room temperature over a 4 hours period
  4. customThe reaction mixture was quenched with dropwise addition of 5% aqueous AcOH solution (10 mL)
  5. additiondiluted with AcOEt (20 mL)
  6. customthe organic phase was separated
  7. extractionThe aqueous layer extracted with AcOEt
  8. washthe combined organic layer was washed with aqueous saturated NaHCO3 solution and brine
  9. dry with materialdried (MgSO4)
  10. customthe solvent was evaporated under reduced pressure
  11. customThe residue obtained
  12. customwas purified by flash column chromatography on silica gel (75% ethyl acetate-hexane)

Sources & evidence

ORD record
ord-d156da80651e4d3c8ee9e83a719b1f52
Source dataset
uspto-grants-2015_08
Patent number
US09102622B2

Reaction notes

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