Benzylhydroxylamine → (R)-(-)-N-(3-t-butyldimethylsilyloxy-2-methylpropylidene)benzylamine-N-oxide

HRID 329788Notes

Reaction equation

HRID 329788 reaction equation
[CH2:1]([NH:8][OH:9])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl-].[Ca+2].[Cl-].[Si:13]([O:20][CH2:21][C@H:22]([CH3:25])[CH:23]=O)([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14]>CCOCC>[Si:13]([O:20][CH2:21][C@H:22]([CH3:25])[CH:23]=[N+:8]([O-:9])[CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)([C:16]([CH3:17])([CH3:18])[CH3:19])([CH3:14])[CH3:15]

Participants

5

Reactant 3

HCID 2794173BenzylhydroxylamineHCID 5284359Calcium ChlorideHCID 10241965(S)-(+)-3-(t-butyldimethylsilyloxy)-2-methylpropanal

Product 1

HCID 88604741(R)-(-)-N-(3-t-butyldimethylsilyloxy-2-methylpropylidene)benzylamine-N-oxideYield 64%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a mixture of N-benzylhydroxylamine prepared by the method as described in J. Am. Chem. Soc., 93, 2897 (1971) (368 mg; 3.0 mmol) and calcium chloride (3.30 mg; 3.0 mmol), anhydrous ether (30 ml) was added in argon stream, and (S)-(+)-3-(t-butyldimethylsilyloxy)-2-methylpropanal (600 mg; 3.0 mmol) was added dropwise thereto at 0° C. Stirring was continued at the same temperature for 1 hour and then at room temperature for 2 hours. The reaction mixture was filtered, and the filtrate was distilled under reduced pressure to remove the solvent. The oily residue was purified by silica gel column chromatography using a mixture of hexane and ethyl acetate (5:5-0:10) to give (R)-(-)-N-(3-t-butyldimethylsilyloxy-2-methylpropylidene)benzylamine-N-oxide (658 mg; 64%).

Workup

  1. customprepared by the method
  2. additionwas added dropwise
  3. customat 0° C
  4. waitat room temperature for 2 hours
  5. filtrationThe reaction mixture was filtered
  6. distillationthe filtrate was distilled under reduced pressure
  7. customto remove the solvent
  8. customThe oily residue was purified by silica gel column chromatography
  9. additiona mixture of hexane and ethyl acetate (5:5-0:10)

Sources & evidence

ORD record
ord-79a8db29f5c945cfa5cbd37f1ce561c1
Source dataset
uspto-grants-1990_01
Patent number
US04892961

Reaction notes

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