O-Methylhydroxylamine hydrochloride → [2R,3R]-2,3-Bis(((1,1-dimethylethyl)di-methylsilyl)oxymethyl)cyclobutanone-O-methyl oxime

HRID 5951

Reaction equation

HRID 5951 reaction equation
[CH3:1][C:2]([Si:5]([CH3:23])([CH3:22])[O:6][CH2:7][C@H:8]1[C@H:11]([CH2:12][O:13][Si:14]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15])[CH2:10][C:9]1=O)([CH3:4])[CH3:3].Cl.[O:25]([NH2:27])[CH3:26]>N1C=CC=CC=1>[CH3:26][O:25][N:27]=[C:9]1[CH2:10][C@@H:11]([CH2:12][O:13][Si:14]([C:17]([CH3:18])([CH3:20])[CH3:19])([CH3:16])[CH3:15])[C@H:8]1[CH2:7][O:6][Si:5]([C:2]([CH3:3])([CH3:4])[CH3:1])([CH3:23])[CH3:22]

Participants

4

Reactant 2

HCID 521874O-Methylhydroxylamine hydrochlorideHCID 54324527[2R,3R]-2,3-Bis(((1,1-dimethylethyl)dimethylsilyl)oxymethyl)cyclobutanone

Product 1

HCID 86747234[2R,3R]-2,3-Bis(((1,1-dimethylethyl)di-methylsilyl)oxymethyl)cyclobutanone-O-methyl oximeYield 75.7%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent2×

Procedure

A solution of 12.317 g (34.9 mmol) of [2R,3R]-2,3-Bis(((1,1-dimethylethyl)dimethylsilyl)oxymethyl)cyclobutanone, from Step E, in 20 mL of pyridine was added to a solution of 3.160 g (37.8 mmol) of methoxylamine hydrochloride in 80 mL of pyridine. After stirring the reaction mixture for 70 min at ambient temperature, it was concentrated to approximately 1/4 of the original volume then diluted with ethyl acetate, washed with saturated aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The residue was purified by flash chromatography on a 5×38 cm silica gel column eluted with 1 L of hexane and 5% acetone in hexane to give 10.228 g (75.7% yield) of the title compound as a mixture of geometrical isomers. .MS DCI-NH3M/Z: 388 (M+H)+.

Workup

  1. concentrationit was concentrated to approximately 1/4 of the original volume
  2. additionthen diluted with ethyl acetate
  3. washwashed with saturated aqueous sodium bicarbonate solution
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flash chromatography on a 5×38 cm silica gel column
  8. washeluted with 1 L of hexane and 5% acetone in hexane

Sources & evidence

ORD record
ord-d480d233dea742e5bf153c3b7f49c34c
Source dataset
uspto-grants-1993_09
Patent number
US05246931

Linked notes

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