Potassium Hydroxide → Ethyl 2-[3-(3-bromophenyl)oxetan-3-yl]acetate

HRID 1920865Notes

Reaction equation

HRID 1920865 reaction equation
[OH-].[K+].[O:3]1[CH2:6][C:5](=[CH:7][C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:4]1.[Br:13][C:14]1[CH:15]=[C:16](B(O)O)[CH:17]=[CH:18][CH:19]=1>O1CCOCC1.[Cl-].[Na+].O>[Br:13][C:14]1[CH:19]=[C:18]([C:5]2([CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:6][O:3][CH2:4]2)[CH:17]=[CH:16][CH:15]=1

Participants

6

Reactant 3

HCID 14797Potassium HydroxideHCID 2734318(3-Bromophenyl)boronic acid2×HCID 53308471Ethyl 2-(oxetan-3-ylidene)acetate

Product 1

HCID 57969689Ethyl 2-[3-(3-bromophenyl)oxetan-3-yl]acetateYield 71.3%

Reagents, catalysts & solvents 2

HCID 312751,4-DioxaneSolvent2×HCID 57417360Sodium chloride; waterSolvent

Procedure

To a solution of [Rh(cod)Cl]2 (171.3 mg, 0.3518 mmol) in 30 mL of dioxane was added aqueous KOH (6.097 mL of 1.5 M, 9.145 mmol) followed by ethyl 2-(oxetan-3-ylidene)acetate (1 g, 7.035 mmol) and a solution of (3-bromophenyl)boronic acid (2.119 g, 10.55 mmol) in 10 mL of dioxane. The reaction was stirred for 30 minutes at room temperature then further (3-bromophenyl)boronic acid (706 mg, 0.5 eq) was added and the reaction stirred overnight. Brine was added and the aqueous layer extracted twice with ethyl acetate. The combined organics were washed with brine and then dried, filtered and concentrated under reduced pressure. The crude product was purified on silica (Companion, 80 g) eluting with 1-20% EtOAc:Petrol ether to give ethyl 2-[3-(3-bromophenyl)oxetan-3-yl]acetate as a yellow oil (1.50 g, 71%).

Workup

  1. stirringthe reaction stirred overnight
  2. extractionthe aqueous layer extracted twice with ethyl acetate
  3. washThe combined organics were washed with brine
  4. customdried
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe crude product was purified on silica (Companion, 80 g)
  8. washeluting with 1-20% EtOAc

Sources & evidence

ORD record
ord-150bda362efe4cc884559b00351d25a9
Source dataset
uspto-grants-2012_05
Patent number
US08173635B2

Reaction notes

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