Triphenylphosphine → Ethyl(5r/s,6r/s)-6-{[(4 fluorophenyl)sulfanyl]methyl}spiro[2.4]-heptane-5-carboxylate

HRID 2222916Notes

Reaction equation

HRID 2222916 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O.O[CH2:35][CH:36]1[CH2:42][C:39]2([CH2:41][CH2:40]2)[CH2:38][CH:37]1[C:43]([O:45][CH2:46][CH3:47])=[O:44].[F:48][C:49]1[CH:54]=[CH:53][C:52]([SH:55])=[CH:51][CH:50]=1>CN(C)C=O>[F:48][C:49]1[CH:54]=[CH:53][C:52]([S:55][CH2:35][CH:36]2[CH2:42][C:39]3([CH2:41][CH2:40]3)[CH2:38][CH:37]2[C:43]([O:45][CH2:46][CH3:47])=[O:44])=[CH:51][CH:50]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 677894-FluorothiophenolHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 91531241Ethyl(5r/s,6r/s)-6-(hydroxymethyl)spiro[2.4]heptane-5-carboxylate

Product 1

HCID 69319826Ethyl(5r/s,6r/s)-6-{[(4 fluorophenyl)sulfanyl]methyl}spiro[2.4]-heptane-5-carboxylate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A solution of triphenylphosphine (240 mg, 910 μmol) in dimethylformamide (1.1 mL) was cooled to 0° C. Diisopropyl azodicarboxylate (0.16 mL, 0.81 mmol) was added and the reaction mixture was stirred for 5 min. Ethyl(5R/S,6R/S)-6-(hydroxymethyl)spiro[2.4]heptane-5-carboxylate (100 mg, 0.54 mmol) and 4-fluorothiophenol (86 μL, 0.81 mmol) in dimethylformamide (1.7 mL) were added. After stirring the reaction mixture for 19 h, it was partitioned between ethyl acetate (30 mL) and 1:1 water:saturated aqueous sodium chloride (30 mL). The product was extracted into ethyl acetate and the combined organics were washed with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate and concentrated using a rotary evaporator. Chromatography of the residue on silica gel eluting with 5:95 ethyl acetate:hexanes provided ethyl(5R/S,6R/S)-6-{[(4-fluorophenyl)sulfanyl]methyl}-spiro[2.4]heptane-5-carboxylate as a colorless oil.

Workup

  1. stirringAfter stirring the reaction mixture for 19 h
  2. customit was partitioned between ethyl acetate (30 mL) and 1:1 water
  3. extractionThe product was extracted into ethyl acetate
  4. washthe combined organics were washed with saturated aqueous sodium chloride solution
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated
  7. customa rotary evaporator

Sources & evidence

ORD record
ord-34c5ab5bf1cb4d088d94cb7579a6e691
Source dataset
uspto-grants-2008_05
Patent number
US07371747B2

Reaction notes

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