Water → tert-butyl (6R,7S)-6-(3,4-dichlorophenyl)-7-ethenyl-1,4-oxazepane-4-carboxylate

HRID 1022648Notes

Reaction equation

[CH2:1]([Li])CCC.CCCCCC.[Cl:12][C:13]1[CH:14]=[C:15]([C@H:20]2[C@H:26]([CH:27]=O)[O:25][CH2:24][CH2:23][N:22]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[CH2:21]2)[CH:16]=[CH:17][C:18]=1[Cl:19].O>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[Cl:12][C:13]1[CH:14]=[C:15]([C@H:20]2[C@H:26]([CH:27]=[CH2:1])[O:25][CH2:24][CH2:23][N:22]([C:29]([O:31][C:32]([CH3:34])([CH3:35])[CH3:33])=[O:30])[CH2:21]2)[CH:16]=[CH:17][C:18]=1[Cl:19]

Participants

Conditions

Temperature: -78 °C

Procedure

A suspension of methyltriphenylphosphonium bromide (3.59 g) in THF (30 mL) was cooled under nitrogen purging to −78° C., and 1.6 M n-butyllithium/hexane solution (5.79 ml) was added. The mixture was warmed to 0° C., and stirred for 20 min, and a solution of tert-butyl (6R,7R)-6-(3,4-dichlorophenyl)-7-formyl-1,4-oxazepane-4-carboxylate (2.89 g) in THF (50 ml) was added. After stirring at 0° C. for 20 min, and at room temperature for 2 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%-30%)) to give the title compound (1.10 g) as a colorless oil.

Workup

temperatureThe mixture was warmed to 0° C.
stirringAfter stirring at 0° C. for 20 min
waitat room temperature for 2 hr
extractionthe mixture was extracted with ethyl acetate
washThe organic layer was washed with brine
dry with materialdried over anhydrous magnesium sulfate
customthe solvent was evaporated
customThe residue was purified by silica gel column chromatography (eluent; hexane:ethyl acetate (0%-30%))

Sources & evidence

ORD record: ord-aec5be62a44e4c53b535f14fa2feb49f
Source dataset: uspto-grants-2014_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08722662B2

Reaction notes

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