p-Toluenesulfonic acid → HCID 57824504, compound

HRID 1943582Notes

Reaction equation

HRID 1943582 reaction equation
C([O:8][C@H:9]1[C@H:14]([CH3:15])[O:13][C@@H:12]([OH:16])[C@H:11]([O:17][CH3:18])[C@@H:10]1[O:19][CH3:20])C1C=CC=CC=1.O[N:22]1[C:26](=[O:27])[CH2:25][CH2:24][C:23]1=[O:28].CC1C=CC(S(O)(=O)=O)=CC=1.[H][H]>C1C=CC=CC=1.CCO.[OH-].[OH-].[Pd+2].O>[OH:8][C@H:9]1[C@H:14]([CH3:15])[O:13][C@@H:12]([O:16][N:22]2[C:26](=[O:27])[CH2:25][CH2:24][C:23]2=[O:28])[C@H:11]([O:17][CH3:18])[C@@H:10]1[O:19][CH3:20]

Participants

9

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 80170N-HydroxysuccinimideHCID 67519186HCID 67519186, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 57824504HCID 57824504, compoundYield 42.2%

Reagents, catalysts & solvents 4

HCID 9942167Palladium hydroxideCatalystHCID 241BenzeneSolventHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

A solution of (2R,3R,4R,5S,6S)-5-benzyloxy-3,4-dimethoxy-6-methyl-tetrahydropyran-2-ol (prepared according to Wu et al., Carbohydr. Res. 1998, 306, 493; 10.5 g, 26.6 mmol), N-hydroxysuccinimide (5.0 g, 50 mmol) and TsOH (250 mg, cat.) in benzene (100 mL) was heated at reflux for 24 h with removal of H2O using a Dean-Stark trap. The brown solution was cooled, filtered, washed with saturated NaHCO3 solution and concentrated. The gummy oil was purified by silica gel chromatography, eluting with 70:30 hexanes-acetone. The pure O-succinimide (7.5 g, 14.5 mmol) was then transferred to a 500-mL Parr hydrogenation apparatus and debenzylated using Pd(OH)2/C (0.95 g) in EtOH (75 mL). The solution, which took up 19 pounds per square inch (psi) of hydrogen over 24 h, was then filtered and concentrated, leaving a solid residue which was recrystallized from EtOH to give a white solid (3.25 g).

Workup

  1. temperatureThe brown solution was cooled
  2. filtrationfiltered
  3. washwashed with saturated NaHCO3 solution
  4. concentrationconcentrated
  5. customThe gummy oil was purified by silica gel chromatography
  6. washeluting with 70:30 hexanes-acetone
  7. customover 24 h
  8. filtrationwas then filtered
  9. concentrationconcentrated
  10. customleaving a solid residue which
  11. customwas recrystallized from EtOH

Sources & evidence

ORD record
ord-c78a2226add24ac78fbeff6c8e88015e
Source dataset
uspto-grants-2013_03
Patent number
US08394774B2

Reaction notes

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