Perchloric Acid → (S)-ethyl 2-tert-butoxy-2-(3,4-dimethyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

HRID 926136Notes

Reaction equation

HRID 926136 reaction equation
[CH3:1][C:2]1[C:3]([C@H:21]([OH:27])[C:22]([O:24][CH2:25][CH3:26])=[O:23])=[C:4]([O:13][S:14]([C:17]([F:20])([F:19])[F:18])(=[O:16])=[O:15])[C:5]2[C:10]([C:11]=1[CH3:12])=[CH:9][CH:8]=[CH:7][CH:6]=2.Cl(O)(=O)(=O)=O>C(OC(C)(C)C)(=O)C>[C:2]([O:27][C@@H:21]([C:3]1[C:2]([CH3:1])=[C:11]([CH3:12])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[C:4]=1[O:13][S:14]([C:17]([F:19])([F:20])[F:18])(=[O:15])=[O:16])[C:22]([O:24][CH2:25][CH3:26])=[O:23])([CH3:3])([CH3:11])[CH3:1]

Participants

4

Reactant 2

HCID 24247Perchloric AcidHCID 89681708(S)-ethyl 2-(3,4-dimethyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-hydroxyacetate

Product 1

HCID 89681707(S)-ethyl 2-tert-butoxy-2-(3,4-dimethyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate

Reagents, catalysts & solvents 1

HCID 10908tert-Butyl acetateSolvent

Procedure

To a solution of (S)-ethyl 2-(3,4-dimethyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-hydroxyacetate (3.80 g, 9.35 mmol) in tert-butyl acetate (94 mL) was added 70% perchloric acid (0.160 mL, 1.37 mmol). The reaction mixture was stirred for 5 h and quenched with solid sodium bicarbonate. The mixture was stirred for 5 minutes and saturated sodium bicarbonate solution was carefully added until pH 7, then diluted with water and extracted with ethyl acetate (2×). The combined organic layer was washed with saturated sodium bicarbonate solution and dried (MgSO4), filtered, concentrated and purified by flash column chromatography (silica gel, 0 to 25% ethyl acetate/hexanes) to give the desired product. 1H NMR (400 MHz, CDCl3) δ 8.08 (dd, J=8.7, 8.7 Hz, 2H), 7.63-7.55 (m, 2H), 5.75 (s, 1H), 4.3-4.1 (m, 2H), 2.63 (s, 3H), 2.47 (s, 3H), 1.20 (s, 3H), 1.17 (t, J=7.4 Hz, 3H).

Workup

  1. customquenched with solid sodium bicarbonate
  2. stirringThe mixture was stirred for 5 minutes
  3. additionsaturated sodium bicarbonate solution was carefully added until pH 7
  4. additiondiluted with water
  5. extractionextracted with ethyl acetate (2×)
  6. washThe combined organic layer was washed with saturated sodium bicarbonate solution
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. custompurified by flash column chromatography (silica gel, 0 to 25% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-c5d97a38d1714dbda90c778cc91cdfc4
Source dataset
uspto-grants-2016_03
Patent number
US09284323B2

Reaction notes

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