Triphenylphosphine → HCID 58446431, compound

HRID 1773765Notes

Reaction equation

HRID 1773765 reaction equation
C([O:9][C@@H:10]1[C@H:14]([O:15]C(=O)C2C=CC=CC=2)[C@@H:13]([CH2:24][O:25]C(=O)C2C=CC=CC=2)[O:12][CH:11]1[C:34]([OH:36])=O)(=O)C1C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1C=C(SSC2N=CC=CC=2)N=CC=1.[F:70][C:71]1[CH:72]=[C:73]([CH:76]=[CH:77][CH:78]=1)[NH:74][CH3:75]>C1COCC1>[F:70][C:71]1[CH:72]=[C:73]([N:74]([CH3:75])[C:34]([CH:11]2[C@H:10]([OH:9])[C@H:14]([OH:15])[C@@H:13]([CH2:24][OH:25])[O:12]2)=[O:36])[CH:76]=[CH:77][CH:78]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 650932,2'-Dipyridyl disulfideHCID 27590113-fluoro-N-methylanilineHCID 69165848(3R,4R,5R)-3,4-Bis(benzoyloxy)-5-(benzoyloxymethyl)tetrahydrofuran-2-carboxylic acid

Product 1

HCID 58446431HCID 58446431, compoundYield 42.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

(3R,4R,5R)-3,4-Bis(benzoyloxy)-5-(benzoyloxymethyl)tetrahydrofuran-2-carboxylic acid (3,4,6-tri-O-benzoyl-2,5-anhydro-D-allonic acid, 2 g, 4 mmol) was dissolved in anhydrous THF (40 mL) under argon atmosphere. To this, triphenylphosphine (2.1 g, 8 mmol) was added and the mixture was stirred until it was dissolved completely. To this clear solution, 2,2′-dipyridyldisulfide (1.8 g, 8 mmol) was added and the mixture was stirred at room temperature for 2 hours, after which, 3-fluoro-N-methylaniline (0.7 g, 5.6 mmol) was added and stirring was continued at room temperature for 16 hours. The solvent was evaporated to dryness, the residue was dissolved in chloroform (150 ml), the solution washed twice with 0.1M NaOH solution (100 mL), twice with 0.2 M HCl solution (100 mL), once with saturated NaHCO3 solution (100 mL), and then dried over Na2SO4. The solution was evaporated to dryness and the residue was re-dissolved in methanolic ammonia (7M solution, 250 mL). The solution was stirred for 16 hours at room temperature and evaporated to dryness. The crude product was purified by silica gel chromatography using a mixture of chloroform-methanol (3:1) and evaporation of the appropriate fractions yielded the title compound as a colorless oil (0.5 g, 1.7 mmol, 42%): MS (ES) m/z 308 [M+Na]+, 284 [M−H]−.

Workup

  1. dissolutionwas dissolved completely
  2. stirringthe mixture was stirred at room temperature for 2 hours
  3. stirringstirring
  4. customThe solvent was evaporated to dryness
  5. dissolutionthe residue was dissolved in chloroform (150 ml)
  6. washthe solution washed twice with 0.1M NaOH solution (100 mL), twice with 0.2 M HCl solution (100 mL), once with saturated NaHCO3 solution (100 mL)
  7. dry with materialdried over Na2SO4
  8. customThe solution was evaporated to dryness
  9. dissolutionthe residue was re-dissolved in methanolic ammonia (7M solution, 250 mL)
  10. stirringThe solution was stirred for 16 hours at room temperature
  11. customevaporated to dryness
  12. customThe crude product was purified by silica gel chromatography
  13. additiona mixture of chloroform-methanol (3:1) and evaporation of the appropriate fractions

Sources & evidence

ORD record
ord-81b662c8261d408da69c42825ccd5ee1
Source dataset
uspto-grants-2016_02
Patent number
US09255121B2

Reaction notes

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