Ethyl Acetate → 1-Azetidinecarboxylic acid, 3-hydroxy-3-(1-hydroxyethyl)-, 1,1-dimethylethyl ester

HRID 1717580Notes

Reaction equation

HRID 1717580 reaction equation
C(=C1C[N:5]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])C1)C.C[N+]1([O-])CC[O:18][CH2:17][CH2:16]1.C(OCC)(=O)C.[CH3:28][C:29]([CH3:31])=[O:30].O>[Os](=O)(=O)(=O)=O>[OH:30][C:29]1([CH:17]([OH:18])[CH3:16])[CH2:31][N:5]([C:7]([O:9][C:10]([CH3:11])([CH3:12])[CH3:13])=[O:8])[CH2:28]1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 82029Methyl morpholine oxideHCID 18366337Propan-2-one--water (1/1)HCID 52180841tert-Butyl 3-ethylideneazetidine-1-carboxylate

Product 1

HCID 670516151-Azetidinecarboxylic acid, 3-hydroxy-3-(1-hydroxyethyl)-, 1,1-dimethylethyl esterYield 63%

Reagents, catalysts & solvents 1

HCID 30318Osmium TetroxideCatalyst

Procedure

1,1-Dimethylethyl 3-ethylideneazetidine-1-carboxylate (506 mg, 2.76 mmol), and 4-methylmorpholine N-oxide (1.04 g, 8.89 mmol) were dissolved in acetone/water (4:1; 30 mL) and osmium tetroxide (2.5 wt. % in t-butanol; 0.2 mL) was added. The solution was stirred at ambient for 5 days, then was quenched with saturated sodium bisulfite (2 mL) and concentrated in vacuo. The residue was partitioned between ethyl acetate and brine. The aqueous portion was extracted with ethyl acetate. The combined organic portion was washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. Column chromatography (silica gel, ethyl acetate) gave 1,1-dimethylethyl 3-hydroxy-3-(1-hydroxyethyl)azetidine-1-carboxylate (375 mg, 1.73 mmol, 63% yield): 1H NMR (400 MHz, CDCl3): 4.00-3.77 (m, 5H), 2.65 (br s, 1H), 1.86, (br s, 1H), 1.44 (s, 9H), 1.25 (d, 3H).

Workup

  1. customwas quenched with saturated sodium bisulfite (2 mL)
  2. concentrationconcentrated in vacuo
  3. customThe residue was partitioned between ethyl acetate and brine
  4. extractionThe aqueous portion was extracted with ethyl acetate
  5. washThe combined organic portion was washed with brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-7f0f37ee1de44a8791143f0fd6df5a99
Source dataset
uspto-grants-2010_09
Patent number
US07803839B2

Reaction notes

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