Acetic Acid → HCID 58313094, compound

HRID 1748860Notes

Reaction equation

HRID 1748860 reaction equation
CC([Si](C)(C)[O:6][CH:7]1[CH2:31][CH2:30][C:10]2([CH2:14][N:13]([C:15]([O:17][CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)=[O:16])[CH:12]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH2:11]2)[CH2:9][CH2:8]1)(C)C.C(O)(=O)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-].C1C=CN=CC=1.F.C([O-])(O)=O.[Na+].C(=O)([O-])[O-].[K+].[K+]>C1COCC1>[OH:6][CH:7]1[CH2:8][CH2:9][C:10]2([CH2:14][N:13]([C:15]([O:17][CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)=[O:16])[CH:12]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH2:11]2)[CH2:30][CH2:31]1

Participants

8

Reactant 6

HCID 176Acetic AcidHCID 11430Potassium CarbonateHCID 64774Pyridine, hydrofluoride (1:1)HCID 516892Sodium BicarbonateHCID 2724141Tetrabutylammonium FluorideHCID 583131673-Ethyl 2-(phenylmethyl) 8-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-2-azaspiro[4.5]decane-2,3-dicarboxylate

Product 1

HCID 58313094HCID 58313094, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 3-ethyl 2-(phenylmethyl) 8-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-2-azaspiro[4.5]decane-2,3-dicarboxylate (111) (5.73 g, 12.05 mmol) in THF (60 mL) was added glacial acetic acid (1.38 mL, 24.0 mmol) followed by TBAF (24 mL) as a 1 M solution in THF. The reaction was stirred at room temperature for 72 h. The reaction was partitioned between EtOAc and water (250 mL) each, the organic layer was separated and washed with saturated NaHCO3 (100 mL) and dried (MgSO4) and concentrated in vacuo. The reaction was found to be incomplete by TLC. The residue was dissolved in dry THF (60 mL), cooled to 0° C. and treated with HF-pyridine (1.6 mL, 18.0 mmol), warmed to room temperature and stirred for 2 h under nitrogen. The reaction was poured into saturated NaHCO3 (100 mL) and solid potassium carbonate was added until gas evolution ceased. Extracted with EtOAc (2×150 mL), the organic layers were combined and washed with 0.1 N HCl (100 mL), dried (MgSO4) and concentrated in vacuo to afford the title compound in quantitative yield as a yellow oil which was used in subsequent reactions without additional purification.

Workup

  1. customThe reaction was partitioned between EtOAc and water (250 mL) each, the organic layer
  2. customwas separated
  3. washwashed with saturated NaHCO3 (100 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated in vacuo
  6. dissolutionThe residue was dissolved in dry THF (60 mL)
  7. temperaturecooled to 0° C.
  8. temperaturewarmed to room temperature
  9. stirringstirred for 2 h under nitrogen
  10. additionwas added until gas evolution
  11. extractionExtracted with EtOAc (2×150 mL)
  12. washwashed with 0.1 N HCl (100 mL)
  13. dry with materialdried (MgSO4)
  14. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-482114ecd8e847538ffded96f92619d1
Source dataset
uspto-grants-2015_10
Patent number
US09150587B2

Reaction notes

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