Dichloromethane → HCID 57425833, compound

HRID 1727306Notes

Reaction equation

HRID 1727306 reaction equation
[CH2:1]([O:3][C:4](=[O:16])[CH:5]=[CH:6][CH2:7][O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[CH3:2].C(Cl)Cl.[Si](OS([C:28]([F:31])(F)F)(=O)=O)(C)(C)C>O>[CH2:1]([O:3][C:4](=[O:16])[CH:28]([F:31])[CH:6]([CH2:7][O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[CH2:5][C:4]([O:3][CH2:1][CH3:2])=[O:16])[CH3:2]

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 65367Trimethylsilyl triflateHCID 53663924Ethyl 4-(benzyloxy)but-2-enoate

Product 1

HCID 57425833HCID 57425833, compoundYield 119.4%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

In a 10 mL flask with 4-benzyloxy-but-2-enoic acid ethyl ester (0.1 g, 0.45 mmol) inside, dry CH2Cl2 3 mL was added under argon. This was cooled to 0° C., TMSOTf (0.08 mL, 0.45 mmol) was added drop by drop. After stirring for 10 min, ethyl α-fluoro silyl enol ether (0.08 g, 0.45 mmol) was added dropwisely at 0° C. This was left stirring at 0° C. for 1.5 hr, at room temperature for 5 hr and refluxing for 25 hr. After cooling to room temperature, H2O was added and the aqueous phase was extracted with CH2Cl2 three times and the combined organic phase was dried over MgSO4 and the solvent was evaporated to give an oily product which was purified by silica gel flash chromatography (Hexane:EtOAc=6:1, Rf=0.42) to give 87.7 mg (59.3%) of the product. 1H NMR (CDCl3, 400 MHz): δ 1.18-1.32 (m, 6H), 2.32-2.54 (m, 2H), 2.77-2.98 (m, 1H), 3.44-3.57 (m, 2H), 4.07-4.30 (m, 4H), 4.45-4.54 (m, 2H), 4.96-5.09 (dd, J=48, 3.2, 1H, minor isomer), 5.10-5.22 (dd, J=48, 3.2, 1H, major isomer), 7.24-7.36 (m, 5H). 13C NMR (CDCl3, 100 MHz): δ 14.23, 30.96-31.02 (d, J=6.0), 32.63, 38.51-38.70 (d, J=19), 60.87, 61.73, 67.94-67.99 (d, J=5.0), 68.60-68.63 (d, J=3.0), 73.29-73.35 (d, J=6.0), 86.96-88.81 (d, J=185), 87.54-89.40 (d, J=186), 127.77, 127.87, 128.54, 137.99-138.04 (d, J=5.0), 168.92-169.42 (t, J=25.8), 171.80-171.85 (d, J=5.0). MS (FAB): expected for C17H23FO5 (M+H)+ 327.36. Found 327.16020. IR (neat) νmax 2983, 2938, 2907, 2872, 1760, 1734, 1455, 1374, 1208, 1183, 1090, 1029, 739, 699.

Workup

  1. waitThis was left
  2. stirringstirring at 0° C. for 1.5 hr, at room temperature for 5 hr
  3. temperaturerefluxing for 25 hr
  4. temperatureAfter cooling to room temperature
  5. extractionthe aqueous phase was extracted with CH2Cl2 three times
  6. dry with materialthe combined organic phase was dried over MgSO4
  7. customthe solvent was evaporated
  8. customto give an oily product which
  9. customwas purified by silica gel flash chromatography (Hexane:EtOAc=6:1, Rf=0.42)

Sources & evidence

ORD record
ord-8d43bbcad7c04f8eb0e92f90cbb35c7a
Source dataset
uspto-grants-2009_02
Patent number
US07495006B2

Reaction notes

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