Dimethyl Sulfoxide → tert-butyl (6R,7R)-6-(3,4-dichlorophenyl)-7-formyl-1,4-oxazepane-4-carboxylate

HRID 1022647Notes

Reaction equation

HRID 1022647 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[Cl:11][C:12]1[CH:13]=[C:14]([C@H:19]2[C@H:25]([CH2:26][OH:27])[O:24][CH2:23][CH2:22][N:21]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[CH2:20]2)[CH:15]=[CH:16][C:17]=1[Cl:18].O>C1COCC1.C(N(CC)CC)C>[Cl:11][C:12]1[CH:13]=[C:14]([C@H:19]2[C@H:25]([CH:26]=[O:27])[O:24][CH2:23][CH2:22][N:21]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[CH2:20]2)[CH:15]=[CH:16][C:17]=1[Cl:18]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 962WaterHCID 65578Oxalyl chlorideHCID 66975324tert-butyl (6R,7R)-6-(3,4-dichlorophenyl)-7-(hydroxymethyl)-1,4-oxazepane-4-carboxylate

Product 1

HCID 86663857tert-butyl (6R,7R)-6-(3,4-dichlorophenyl)-7-formyl-1,4-oxazepane-4-carboxylateYield 96.9%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8471TriethylamineSolvent

Procedure

To a solution of oxalyl chloride (1.52 g) in THF (20 mL) was added dimethyl sulfoxide (1.87 g) at −78° C., and the mixture was stirred for 20 min. A solution of tert-butyl (6R,7R)-6-(3,4-dichlorophenyl)-7-(hydroxymethyl)-1,4-oxazepane-4-carboxylate (3.0 g) in THF (10 mL) and triethylamine (7.78 mL) were added at −78° C., and the mixture was warmed to room temperature and stirred for 1 hr. Water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, and dried over anhydrous magnesium sulfate, and the solvent was evaporated. The residue was purified by silica gel column chromatography (eluent; hexane:ethyl acetate (0%-50%)) to give the title compound (2.89 g) as a colorless solid.

Workup

  1. stirringstirred for 1 hr
  2. extractionthe mixture was extracted with ethyl acetate
  3. washThe organic layer was washed with brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customthe solvent was evaporated
  6. customThe residue was purified by silica gel column chromatography (eluent; hexane:ethyl acetate (0%-50%))

Sources & evidence

ORD record
ord-eae05214f4074e90ab220ec57e287eb7
Source dataset
uspto-grants-2014_05
Patent number
US08722662B2

Reaction notes

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