Perchloric Acid → (S)-ethyl 2-tert-butoxy-2-(1-(4-chlorophenyl)-3-methyl-6-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

HRID 514060Notes

Reaction equation

HRID 514060 reaction equation
Cl(O)(=O)(=O)=O.[Cl:6][C:7]1[CH:12]=[CH:11][C:10]([C:13]2[C:22]3[C:17](=[CH:18][C:19]([O:23][S:24]([C:27]([F:30])([F:29])[F:28])(=[O:26])=[O:25])=[CH:20][CH:21]=3)[CH:16]=[C:15]([CH3:31])[C:14]=2[C@H:32]([OH:38])[C:33]([O:35][CH2:36][CH3:37])=[O:34])=[CH:9][CH:8]=1.C([O-])(O)=O.[Na+]>C(OC(C)(C)C)(=O)C>[C:10]([O:38][C@@H:32]([C:14]1[C:15]([CH3:31])=[CH:16][C:17]2[C:22](=[CH:21][CH:20]=[C:19]([O:23][S:24]([C:27]([F:30])([F:29])[F:28])(=[O:26])=[O:25])[CH:18]=2)[C:13]=1[C:10]1[CH:9]=[CH:8][C:7]([Cl:6])=[CH:12][CH:11]=1)[C:33]([O:35][CH2:36][CH3:37])=[O:34])([CH3:13])([CH3:11])[CH3:9]

Participants

5

Reactant 3

HCID 24247Perchloric AcidHCID 516892Sodium Bicarbonate2×HCID 86691546(S)-ethyl 2-(1-(4-chlorophenyl)-3-methyl-6-(trifluoromethylsulfonyloxy) naphthalen-2-yl)-2-hydroxyacetate

Product 1

HCID 86691548(S)-ethyl 2-tert-butoxy-2-(1-(4-chlorophenyl)-3-methyl-6-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetateYield 116.3%

Reagents, catalysts & solvents 1

HCID 10908tert-Butyl acetateSolvent

Procedure

Perchloric acid (70%, 0.28 mL, 3.2 mmol) was added to a solution of (S)-ethyl 2-(1-(4-chlorophenyl)-3-methyl-6-(trifluoromethylsulfonyloxy) naphthalen-2-yl)-2-hydroxyacetate (0.82 g, 1.6 mmol) in tert-butyl acetate (5 mL) at room temperature. After 3 h, solid NaHCO3 was added and the slurry stirred vigorously for 30 min. Saturated NaHCO3 was added slowly until the mixture was pH ˜8. Following extraction of the organic layer with EtOAc, the combined organics were washed with brine, dried over anhydrous MgSO4 and concentrated in vacuo. The resulting residue was purified by Yamazen column chromatography (0-35% EtOAc/Hex) to produce 0.52 g (57%) of the title compound as an amorphous solid. 1H-NMR: 400 MHz, (CDCl3) δ: 7.69 (s, 1H); 7.66 (d, J=2.4 Hz, 1H); 7.51 (m, 2H); 7.44 (m, 1H); 7.34 (d, J=9.4 Hz, 1H); 7.27 (m, 1H); 7.15 (dd, J=9.4, 2.4 Hz, 1H); 5.12 (s, 1H); 4.17 (m, 2H); 2.63 (s, 3H); 1.23 (t, J=7.2 Hz, 3H); 1.01 (s, 9H).

Workup

  1. extractionextraction of the organic layer with EtOAc
  2. washthe combined organics were washed with brine
  3. dry with materialdried over anhydrous MgSO4
  4. concentrationconcentrated in vacuo
  5. customThe resulting residue was purified by Yamazen column chromatography (0-35% EtOAc/Hex)

Sources & evidence

ORD record
ord-830b9125f629475c84cb7d29bb5b6adf
Source dataset
uspto-grants-2015_08
Patent number
US09102614B2

Reaction notes

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