Cesium carbonate → HCID 18790107, compound

HRID 1107139Notes

Reaction equation

HRID 1107139 reaction equation
C(=O)([O-])[O-].[Cs+].[Cs+].[CH3:7][O:8][C:9]1[CH:10]=[C:11]([SH:17])[CH:12]=[CH:13][C:14]=1[O:15][CH3:16].[C:18]1([S:24]([CH2:27][CH2:28][CH:29]2[CH:32]([CH2:33][CH2:34][CH2:35][CH2:36][C:37]3[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=3)[O:31][C:30]2=[O:43])(=[O:26])=[O:25])[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>CN(C=O)C.C(OCC)C>[C:18]1([S:24]([CH2:27][CH2:28][CH:29]([CH:32]([S:17][C:11]2[CH:12]=[CH:13][C:14]([O:15][CH3:16])=[C:9]([O:8][CH3:7])[CH:10]=2)[CH2:33][CH2:34][CH2:35][CH2:36][C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=2)[C:30]([OH:43])=[O:31])(=[O:26])=[O:25])[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 1365393,4-Dimethoxybenzene-1-thiolHCID 18790043HCID 18790043, compound

Product 1

HCID 18790107HCID 18790107, compoundYield 78.4%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent2×

Procedure

To a vigorously stirring suspension of cesium carbonate (0.88 g, 2.69 mmol) in anhydrous DMF (10 mL) under a nitrogen atmosphere is added 3,4-dimethoxythiophenol (0.45 g, 2.69 mmol) in a dropwise fashion. The white heterogeneous mixture is stirred for 15 minutes then a solution containing (-)-3-(2-benzenesulfonylethyl)-4-(4-phenylbutyl)-oxetan-2-one (0.50 g, 1.34 mmol) in anhydrous DMF (4 mL) is added. The pale yellow heterogeneous mixture is stirred at room temperature for 2.5 hours then partitioned between water (50 mL) and diethyl ether (50 mL). Aqueous HCl (1 N, 5 mL) is added and the layers are separated. The aqueous phase is extracted with diethyl ether (2×20 mL) and the combined organic extracts are washed with water (10×10 mL), brine (20 mL), dried over anhydrous MgSO4, filtered and concentrated to afford a pale yellow oil. The crude product is chromatographed on silica gel (CH2Cl2 →CH2Cl2 :MeOH, 19:1) to afford a colorless oil which is dissolved in diethyl ether (100 mL) and washed with water (10×30 mL) to remove residual DMF. The organic phase is washed with brine (30 mL), dried over anhydrous MgSO4, filtered and concentrated to afford (-)-2-(2-benzenesulfonylethyl)-3-(3,4-dimethoxyphenyl-sulfanyl)-7-phenylheptanoic acid (0.57 g, 78%) as a white foam. TLC analysis [hexane/EtOAc, 2:1, Rf (lactone)=0.65, Rf (acid)=0.05]. [α]23D -35.3° (c 1.0, CHCl3); 1H NMR (300 MHz, CDCl3) δ 1.31-1.70 (m, 6H), 2.00 (m, 1H), 2.30 (m, 1H), 2.56 (m, 3H), 2.95 (m, 1H), 3.25 (m, 2H), 3.84 (s, 3H), 3.85 (s, 3H), 6.77 (d, J=8.2 Hz, 1H), 6.95 (m, 2H), 7.15 (m, 3H), 7.25 (m, 2H), 7.55 (m, 2H), 7.65 (m, 1H), 7.90 (m, 2H) ppm. Mass spectrum (FAB) m/z 542 (M)+.

Workup

  1. stirringThe white heterogeneous mixture is stirred for 15 minutes
  2. additionis added
  3. stirringThe pale yellow heterogeneous mixture is stirred at room temperature for 2.5 hours
  4. customthen partitioned between water (50 mL) and diethyl ether (50 mL)
  5. additionAqueous HCl (1 N, 5 mL) is added
  6. customthe layers are separated
  7. extractionThe aqueous phase is extracted with diethyl ether (2×20 mL)
  8. washthe combined organic extracts are washed with water (10×10 mL), brine (20 mL)
  9. dry with materialdried over anhydrous MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customto afford a pale yellow oil
  13. customThe crude product is chromatographed on silica gel (CH2Cl2 →CH2Cl2 :MeOH, 19:1)
  14. customto afford a colorless oil which
  15. washwashed with water (10×30 mL)
  16. customto remove residual DMF
  17. washThe organic phase is washed with brine (30 mL)
  18. dry with materialdried over anhydrous MgSO4
  19. filtrationfiltered
  20. concentrationconcentrated

Sources & evidence

ORD record
ord-1c120e57c7f647d486570a3b51815486
Source dataset
uspto-grants-2000_05
Patent number
US06057369

Reaction notes

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