Perchloric Acid → (S)-ethyl 2-(6-bromo-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-tert-butoxyacetate

HRID 926185Notes

Reaction equation

HRID 926185 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8]([O:12][S:13]([C:16]([F:19])([F:18])[F:17])(=[O:15])=[O:14])=[C:7]([C@H:20]([OH:26])[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:6]([CH3:27])=[CH:5]2.Cl(O)(=O)(=O)=O>C(OC(=O)C)(C)(C)C>[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8]([O:12][S:13]([C:16]([F:18])([F:17])[F:19])(=[O:15])=[O:14])=[C:7]([C@H:20]([O:26][C:4]([CH3:9])([CH3:5])[CH3:3])[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:6]([CH3:27])=[CH:5]2

Participants

4

Reactant 2

HCID 24247Perchloric AcidHCID 89681790(S)-ethyl 2-(6-bromo-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-hydroxyacetate

Product 1

HCID 89681724(S)-ethyl 2-(6-bromo-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-tert-butoxyacetate

Reagents, catalysts & solvents 1

HCID 10908tert-Butyl acetateSolvent

Procedure

To a solution of (S)-ethyl 2-(6-bromo-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-hydroxyacetate (2 g, 4.26 mmol) in tert-butylacetate (30 mL) was added 70% perchloric acid (1.10 mL, 4.69 mmol). The reaction mixture was stirred for 2.5 hours and quenched with solid sodium bicarbonate and stirred for 45 minutes. Water and solid sodium bicarbonate were carefully added and stirred for another 15 minutes. The mixture was diluted with ethyl acetate, washed with saturated bicarbonate solution (2×), brine, dried (MgSO4), filtered, concentrated and purified by flash column chromatography (silica gel, 0 to 20% ethyl acetate/hexanes) to give the desired compound. 1H NMR (400 MHz, CDCl3) δ: 7.96 (s, 1H), 7.90 (d, J=10.2 Hz, 1H), 7.62 (d, J=9.2 Hz, 1H), 7.58 (s, 1H), 5.90 (s, 1H), 4.26-4.08 (m, 2H), 2.53 (s, 3H), 1.20 (s, 9H), 1.17 (t, J=7.1 Hz, 3H).

Workup

  1. customquenched with solid sodium bicarbonate
  2. stirringstirred for 45 minutes
  3. additionWater and solid sodium bicarbonate were carefully added
  4. stirringstirred for another 15 minutes
  5. additionThe mixture was diluted with ethyl acetate
  6. washwashed with saturated bicarbonate solution (2×), brine
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. custompurified by flash column chromatography (silica gel, 0 to 20% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-202739d6a1ae4f689bc425e0e44998be
Source dataset
uspto-grants-2016_03
Patent number
US09284323B2

Reaction notes

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