Triethylamine → Methyl (3E)-4-(2-{(1R)-1-[(2R)-oxiran-2-yl methoxy]ethyl}phenyl)but-3-enoate

HRID 1927293Notes

Reaction equation

HRID 1927293 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C@H:8]([O:10][CH2:11][C@H:12]1[CH2:14][O:13]1)[CH3:9].[C:15]([O:20][CH3:21])(=[O:19])[CH2:16][CH:17]=[CH2:18].CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CC)CC)C>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[O:13]1[CH2:14][C@@H:12]1[CH2:11][O:10][C@@H:8]([C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1/[CH:18]=[CH:17]/[CH2:16][C:15]([O:20][CH3:21])=[O:19])[CH3:9]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 77314Methyl 3-butenoateHCID 80271Tri-o-tolylphosphineHCID 58981243(2R)-2-[[(1R)-1-(2-bromophenyl)ethoxy]methyl]oxirane

Product 1

HCID 58572466Methyl (3E)-4-(2-{(1R)-1-[(2R)-oxiran-2-yl methoxy]ethyl}phenyl)but-3-enoateYield 23%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Procedure

Under an argon atmosphere, a mixture of (2R)-2-{[(1R)-1-(2-bromophenyl)ethoxy]methyl}oxirane (1.00 g, 3.89 mmol) described in WO 2004/094362, methyl but-3-enoate (497 μL, 4.67 mmol), palladium acetate (II) (44 mg, 0.19 mmol), tris(2-methylphenyl)phosphine (59 mg, 0.19 mmol), and triethylamine (0.65 mL, 4.67 mmol) in acetonitrile (10 mL) was stirred with heating under reflux for 3 hours. The reaction solution was cooled to room temperature, filtered through Celite, and washed with acetonitrile. The solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane/ethyl acetate=4/1) to give the title compound as a yellow oily substance (246 mg, yield 23%).

Workup

  1. temperaturewith heating
  2. temperatureunder reflux for 3 hours
  3. filtrationfiltered through Celite
  4. washwashed with acetonitrile
  5. distillationThe solvent was distilled off under reduced pressure
  6. customThe residue was purified by silica gel column chromatography (n-hexane/ethyl acetate=4/1)

Sources & evidence

ORD record
ord-4effa9f8ab024aa187a452f46ad47ded
Source dataset
uspto-grants-2012_05
Patent number
US08183272B2

Reaction notes

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