Methyl vinyl ketone → Tert-butyl 9-oxo-3-azaspiro[5.5]undec-7-ene-3-carboxylate

HRID 1253716Notes

Reaction equation

[OH-].[K+].[CH:3]([CH:5]1[CH2:10][CH2:9][N:8]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH2:7][CH2:6]1)=O.[CH:18]([C:20]([CH3:22])=[O:21])=[CH2:19]>C(O)C.C1COCC1>[O:21]=[C:20]1[CH2:18][CH2:19][C:5]2([CH2:10][CH2:9][N:8]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH2:7][CH2:6]2)[CH:3]=[CH:22]1

Participants

Conditions

Temperature: 25 °C

Procedure

3 N KOH in ethanol (7.5 ml) was added to mixture of tert-butyl 4-formylpiperidine-1-carboxylate (60.0 mmol, 1.0 eq.) and methyl vinyl ketone (70.0 mmol, 1.3 eq.) in THF (100 ml) at 0° C. and the mixture was then stirred at 25° C. for 16 h. The solvent was evaporated under reduced pressure and the residue diluted with water (100 ml) and KHSO4 solution at 0° C. The aqueous layer was extracted with MC (2×150 ml). The combined organic layers were washed with brine (100 ml) and dried over sodium sulfate. The solvent was evaporated under reduced pressure and the crude product was purified by silica gel column chromatography eluting with 10-12% ethyl acetate in hexanes to give the desired product as a light brown sticky solid. Yield: 25%

Workup

customThe solvent was evaporated under reduced pressure
additionthe residue diluted with water (100 ml) and KHSO4 solution at 0° C
extractionThe aqueous layer was extracted with MC (2×150 ml)
washThe combined organic layers were washed with brine (100 ml)
dry with materialdried over sodium sulfate
customThe solvent was evaporated under reduced pressure
customthe crude product was purified by silica gel column chromatography
washeluting with 10-12% ethyl acetate in hexanes

Sources & evidence

ORD record: ord-23a2e45b535147b0aaaf324cc8c6e981
Source dataset: uspto-grants-2013_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08455475B2

Reaction notes

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