Sodium Thiosulfate → HCID 86691561, compound

HRID 514114Notes

Reaction equation

HRID 514114 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]([CH:20]([OH:26])[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:3]=1[CH3:27].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.[O-]S([O-])(=S)=O.[Na+].[Na+]>C(Cl)Cl.O>[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:17])[F:18])(=[O:14])=[O:15])=[C:4]([C:20](=[O:26])[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:3]=1[CH3:27]

Participants

6

Reactant 3

HCID 24477Sodium ThiosulfateHCID 159087TriacetoxyperiodinaneHCID 86691559HCID 86691559, compound

Product 1

HCID 86691561HCID 86691561, compoundYield 70.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of ethyl 2-(4-fluoro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-hydroxyacetate (˜1.54 g, 3.76 mmol) in DCM (60 mL) was treated with Dess-Martin periodinane (1.91 g, 4.51 mmol) at 23° C. After 4 h, the orange reaction was slowly added to 10% Na2S2O3 (28 mL) at 23° C. After 5 min of stirring, the reaction was diluted with H2O (40 mL) and extracted with DCM (3×20 mL). 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/hexanes 1:4) giving the desired product (1.08 g, 70% yield over 2 steps from ethyl 2-tert-butoxy-2-(4-fluoro-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)acetate). 1H NMR (400 MHz, CDCl3) δ 8.16-8.08 (m, 2H), 7.76-7.68 (m, 2H), 4.41 (q, J=7.1 Hz, 2H), 2.39 (d, JHF=3.2 Hz, 3H), 1.40 (t, J=7.1 Hz, 3H). 19F NMR (377 MHz, CDCl3) δ−122.3 (app. s, 1F), −73.3 (s, 3F).

Workup

  1. customthe orange reaction
  2. extractionextracted with DCM (3×20 mL)
  3. dry with materialCombined organic layers were dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. dissolutionThe residue was dissolved in benzene
  7. custompurified by flash chromatography (hexane→ethyl acetate/hexanes 1:4)

Sources & evidence

ORD record
ord-7c6f0067aba7453fb8d37bd0ca7a5108
Source dataset
uspto-grants-2015_08
Patent number
US09102614B2

Reaction notes

Loading…