O-Xylene → HCID 117873679, compound

HRID 517388Notes

Reaction equation

HRID 517388 reaction equation
O[C@@H:2]1[C@H:6]([CH2:7]/[CH:8]=[CH:9]\[CH2:10][CH2:11][CH2:12][C:13]([OH:15])=[O:14])[C@@H:5]([CH2:16][CH2:17][C@@H:18]([O:27][CH:28]2[CH2:33][CH2:32][CH2:31][CH2:30][O:29]2)[CH2:19]CC2C=CC=CC=2)[C@H:4]([O:34][CH:35]2[CH2:40][CH2:39][CH2:38][CH2:37][O:36]2)[CH2:3]1.C1C=C(SSC2N=CC=CC=2)N=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:74]1([CH3:81])[C:75](C)=[CH:76][CH:77]=[CH:78][CH:79]=1>>[C:74]1([CH2:81][CH2:19][C@H:18]([O:27][CH:28]2[CH2:33][CH2:32][CH2:31][CH2:30][O:29]2)[CH2:17][CH2:16][C@@H:5]2[C@@H:6]3[C@@H:2]([O:14][C:13](=[O:15])[CH2:12][CH2:11][CH2:10][CH:9]=[CH:8][CH2:7]3)[CH2:3][C@H:4]2[O:34][CH:35]2[CH2:40][CH2:39][CH2:38][CH2:37][O:36]2)[CH:79]=[CH:78][CH:77]=[CH:76][CH:75]=1

Participants

5

Reactant 4

HCID 7237O-XyleneHCID 11776TriphenylphosphineHCID 650932,2'-Dipyridyl disulfideHCID 42604334HCID 42604334, compound

Product 1

HCID 117873679HCID 117873679, compoundYield 68%

Procedure

A solution of (Z)-7-((1R,2R,3R,5S)-5-hydroxy-2-((3R)-5-phenyl-3-((tetrahydro-2H-pyran-2-yl)oxy)pentyl)-3-((tetrahydro-2H-pyran-2-yl)oxy)cyclopentyl)hept-5-enoic acid (52 g from Example 26) in xylene (250 mL) was treated with 2,2′-dipyridyl disulfide (28.9 g, 131.2 mmol) and triphenylphosphine (39.2 g, 149.5 mmol). This mixture was then stirred for 2 hr at room temperature under an atmosphere of nitrogen. The resulting mixture was heated to 80° C. for 18 hr (TLC monitoring), followed by removal of xylene under reduced pressure. The residue was diluted with saturated aqueous solution of sodium bicarbonate (200 mL) and extracted with ethyl acetate (200 mL). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give 80.0 g of crude product. The crude product was purified by column chromatography providing 17.1 g of the title compound (68.0% yield, 3 steps).

Workup

  1. temperatureThe resulting mixture was heated to 80° C. for 18 hr (TLC monitoring)
  2. customfollowed by removal of xylene under reduced pressure
  3. additionThe residue was diluted with saturated aqueous solution of sodium bicarbonate (200 mL)
  4. extractionextracted with ethyl acetate (200 mL)
  5. dry with materialThe organic layer was dried over magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customto give 80.0 g of crude product
  8. customThe crude product was purified by column chromatography

Sources & evidence

ORD record
ord-71155c6bd9274835b6c954e9e5f529ed
Source dataset
uspto-grants-2015_08
Patent number
US09115109B2

Reaction notes

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