Trifluoromethanesulfonate → HCID 58703563, compound

HRID 1179467Notes

Reaction equation

HRID 1179467 reaction equation
Br[C:2]1[CH:7]=[C:6]([O:8][CH2:9][O:10][CH3:11])[CH:5]=[C:4]([CH2:12][O:13][CH3:14])[C:3]=1[O:15][CH2:16][O:17][CH3:18].C1([Li])C=CC=CC=1.[CH3:26][O:27][C:28]([C:30]1[CH2:34][CH2:33][CH2:32][C:31]=1OS(C(F)(F)F)(=O)=O)=[O:29].[O-]S(C(F)(F)F)(=O)=O>C1COCC1.C(OCCCC)CCC.CCOCC.[Cl-].[Cl-].[Zn+2].[O-]S([O-])(=O)=O.[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:26][O:27][C:28]([C:30]1[CH2:34][CH2:33][CH2:32][C:31]=1[C:2]1[CH:7]=[C:6]([O:8][CH2:9][O:10][CH3:11])[CH:5]=[C:4]([CH2:12][O:13][CH3:14])[C:3]=1[O:15][CH2:16][O:17][CH3:18])=[O:29]

Participants

11

Reactant 4

HCID 2758875TrifluoromethanesulfonateHCID 10880291methyl 2-(((trifluoromethyl)sulfonyl)oxy)cyclopent-1-enecarboxylateHCID 58703560HCID 58703560, compoundHCID 178506676HCID 178506676, compound

Product 1

HCID 58703563HCID 58703563, compoundYield 56%

Reagents, catalysts & solvents 6

HCID 24424Zinc SulfateCatalystHCID 3007855ZincchlorideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×HCID 8909Butyl etherSolvent

Conditions

Temperature
-70 °C

Procedure

Purge a solution of 1-bromo-2,5-bis-methoxymethoxy-3-methoxymethyl-benzene (2.76 g, 8.59 mmol) in THF (17 mL) with nitrogen and cool to −70° C. Clowly add a solution of phenyllithium (4.3 mL of a 2.0 M solution in dibutyl ether, 8.59 mmol) to the cooled solution, keeping the temperature below −60° C. After 35 minutes, add a solution of ZnCl2 (8.6 mL of a 1.0 M solution in Et2O, 8.59 mmol) and warm the reaction to 0° C. Purge a solution of 2-trifluoromethanesulfonyloxy-cyclopent-1-enecarboxylic acid methyl ester (2.36 g, 8.59 mmol) in THF (17 mL) with nitrogen. To the cooled zincate solution, add Pd(PPh3)4 (0.496 g, 0.430 mmol) followed by the triflate solution. Heat this mixture to 50° C. overnight then cool to room temperature. Quench the reaction with H2O and extract with EtOAc (3×50 mL). Combine the organic extracts, dry (Na2SO4), filter and concentrate. Purify the crude material using silica gel chromatography eluting with Hex:EtOAc (75:25, then 50:50) to afford the subtitled product (1.76 g, 56%) as an oil. 1H NMR (CDCl3) δ 1.95-2.05 (m, 2H), 2.78-2.85 (m, 4H), 3.42 (s, 3H), 3.47 (s, 6H), 3.57 (s, 3H), 4.51 (s, 2H), 4.80 (s, 2H), 5.12 (s, 2H), 6.74 (d, J=3.1 Hz, 1H), 7.04 (d, J=3.1 Hz, 1H).

Workup

  1. customthe temperature below −60° C
  2. temperaturewarm
  3. customthe reaction to 0° C
  4. temperatureHeat this mixture to 50° C. overnight
  5. temperaturethen cool to room temperature
  6. customQuench
  7. customthe reaction with H2O
  8. extractionextract with EtOAc (3×50 mL)
  9. dry with materialCombine the organic extracts, dry (Na2SO4)
  10. filtrationfilter
  11. concentrationconcentrate
  12. customPurify the crude material
  13. washeluting with Hex

Sources & evidence

ORD record
ord-d639be0097a548e9ac9341fcec8634b8
Source dataset
uspto-grants-2007_10
Patent number
US07279499B2

Reaction notes

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