Perchloric Acid → HCID 86691563, compound

HRID 514116Notes

Reaction equation

HRID 514116 reaction equation
[F:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([O:12][S:13]([C:16]([F:19])([F:18])[F:17])(=[O:15])=[O:14])=[C:4]([C@H:20]([OH:26])[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:3]=1[CH3:27].Cl(O)(=O)(=O)=O.C([O-])(O)=O.[Na+]>C(OC(C)(C)C)(=O)C>[C:3]([O:26][C@@H:20]([C:4]1[C:3]([CH3:27])=[C:2]([F:1])[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]=1[O:12][S:13]([C:16]([F:17])([F:19])[F:18])(=[O:14])=[O:15])[C:21]([O:23][CH2:24][CH3:25])=[O:22])([CH3:27])([CH3:4])[CH3:2]

Participants

5

Reactant 3

HCID 24247Perchloric AcidHCID 516892Sodium BicarbonateHCID 86691562HCID 86691562, compound

Product 1

HCID 86691563HCID 86691563, compoundYield 162.2%

Reagents, catalysts & solvents 1

HCID 10908tert-Butyl acetateSolvent

Procedure

A solution of (S)-ethyl 2-(4-fluoro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-hydroxyacetate (1.02 g, 2.49 mmol) in tert-butyl acetate (20 mL) was treated with 70% HClO4 (20 μL) at 23° C.). After 5 h, the reaction was added slowly over 5 min to saturated NaHCO3 (40 mL). The resulting system was extracted with DCM (3×30 mL). The combined organic layers were dried (Na2SO4), filtered, and concentrated. The residue was dissolved in benzene. The solution was wet-loaded onto a 40 g “gold” ISCO silica gel column and purified by flash chromatography (hexane→ethyl acetate/hexane 1:4) giving the desired product (942 mg, 81% yield). 1H NMR (400 MHz, CDCl3) δ 8.11-8.02 (m, 2H), 7.65-7.60 (m, 2H), 5.72 (s, 1H), 4.25-4.13 (m, 2H), 2.45 (d, JHF=3.2 Hz, 3H), 1.21 (s, 9H), 1.18 (t, J=7.0 Hz, 3H). 19F NMR (377 MHz, CDCl3) δ−123.1 (ap s, 1F), −73.3 (s, 3F).

Workup

  1. extractionThe resulting system was extracted with DCM (3×30 mL)
  2. dry with materialThe combined organic layers were dried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. dissolutionThe residue was dissolved in benzene
  6. custompurified by flash chromatography (hexane→ethyl acetate/hexane 1:4)

Sources & evidence

ORD record
ord-7399862ef4534ecfadd892146a25dd55
Source dataset
uspto-grants-2015_08
Patent number
US09102614B2

Reaction notes

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