Trifluoromethanesulfonic acid → Ethyl 1-[(4-nitrophenyl)sulfonyl]-8-oxa-1-azaspiro[4.5]decane-2-carboxylate

HRID 1748882Notes

Reaction equation

HRID 1748882 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([S:10]([NH:13][CH:14]([CH2:20][CH:21]=[C:22]2[CH2:27][CH2:26][O:25][CH2:24][CH2:23]2)[C:15]([O:17][CH2:18][CH3:19])=[O:16])(=[O:12])=[O:11])=[CH:6][CH:5]=1)([O-:3])=[O:2].FC(F)(F)S(O)(=O)=O>C(Cl)(Cl)Cl.ClCCl>[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([S:10]([N:13]2[C:22]3([CH2:27][CH2:26][O:25][CH2:24][CH2:23]3)[CH2:21][CH2:20][CH:14]2[C:15]([O:17][CH2:18][CH3:19])=[O:16])(=[O:11])=[O:12])=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

5

Reactant 2

HCID 62406Trifluoromethanesulfonic acidHCID 58313106ethyl 2-{[(4-nitrophenyl)sulfonyl]amino}-4-(tetrahydro-4H-pyran-4-ylidene)butanoate

Product 1

HCID 58313109Ethyl 1-[(4-nitrophenyl)sulfonyl]-8-oxa-1-azaspiro[4.5]decane-2-carboxylateYield 79%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of ethyl 2-{[(4-nitrophenyl)sulfonyl]amino}-4-(tetrahydro-4H-pyran-4-ylidene)butanoate (164) (1.87 g, 4.7 mmol) in anhydrous chloroform (47 mL) was added trifluoromethanesulfonic acid (0.2 mL, 2.3 mmol) and the reaction stirred at room temperature under nitrogen for 4 h. The reaction was diluted with dichloromethane and washed with saturated NaHCO3 and the organic layer dried over MgSO4 and concentrated in vacuo. The residue was purified by silica gel chromatography eluting with 10-70% hexanes/EtOAc to afford the title compound as a white solid (1.47 g, 79% yield). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 8.19-8.36 (m, 2H) 8.08 (d, J=8.8 Hz, 2H) 4.52 (dd, J=8.5, 2.1 Hz, 1H) 3.99-4.14 (m, 2H) 3.87-3.99 (m, 2H) 3.21-3.49 (m, 2H) 2.58-2.78 (m, 2H) 2.10-2.30 (m, 2H) 1.89-2.06 (m, 2H) 1.77 (dd, J=13.0, 2.1 Hz, 1H) 1.35 (dd, J=12.9, 1.6 Hz, 1H) 1.22 (t, J=7.1 Hz, 3H). LC-MS ESI (M+H)+=399.47.

Workup

  1. washwashed with saturated NaHCO3
  2. dry with materialthe organic layer dried over MgSO4
  3. concentrationconcentrated in vacuo
  4. customThe residue was purified by silica gel chromatography
  5. washeluting with 10-70% hexanes/EtOAc

Sources & evidence

ORD record
ord-9c7a3c58e15d4e5fa5e2044cc93b553d
Source dataset
uspto-grants-2015_10
Patent number
US09150587B2

Reaction notes

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