Pyridine → HCID 57684693, compound

HRID 425052Notes

Reaction equation

HRID 425052 reaction equation
[C:1]([O:4][C@H:5]1[C@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@H:8]([C:19]2[CH:24]=[CH:23][C:22]([Cl:25])=[C:21]([CH2:26][C:27]3[CH:32]=[CH:31][C:30]([C:33](=O)[CH3:34])=[CH:29][CH:28]=3)[CH:20]=2)[O:7][C@@H:6]1[CH2:36][O:37][C:38](=[O:40])[CH3:39])(=[O:3])[CH3:2].N1C=CC=C[CH:42]=1.CC(OC(C)=O)=O>C1(C)C=CC=CC=1.C(Cl)Cl.CN(C1C=CN=CC=1)C>[C:1]([O:4][C@H:5]1[C@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@H:8]([C:19]2[CH:24]=[CH:23][C:22]([Cl:25])=[C:21]([CH2:26][C:27]3[CH:28]=[CH:29][C:30]([C:33]([CH3:42])=[CH2:34])=[CH:31][CH:32]=3)[CH:20]=2)[O:7][C@@H:6]1[CH2:36][O:37][C:38](=[O:40])[CH3:39])(=[O:3])[CH3:2]

Participants

7

Reactant 3

HCID 1049PyridineHCID 7918Acetic AnhydrideHCID 59557758HCID 59557758, compound

Product 1

HCID 57684693HCID 57684693, compound

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1140TolueneSolvent2×HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of Ph3PMeI (378 mg, 0.935 mmol) in toluene (3 mL) was added KN(TMS)2 (0.5 M, 1.8 mL) dropwise. After stirring for 40 min, (2R,3R,4R,5S,6S)-2-(acetoxymethyl)-6-(3-(4-acetylbenzyl)-4-chlorophenyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate (intermediate AY) (360 mg, 0.626 mmol) in toluene (5 mL) was added. After stirring overnight, the reaction was quenched with a saturated solution of NaHCO3. The mixture was extracted 3× with AcOEt. The combined organic extracts were washed 1× with brine prior to drying over Na2SO4. Concentration of the solution gave an oily residue, which was redissolved in 3 mL of CH2Cl2, and then 0.2 mL of pyridine (2.47 mmol), 0.23 mL of Ac2O (2.44 mmol) and DMAP (catalytic quantity) were added. The mixture was stirred for 2 h at room temperature. Additional CH2Cl2 (20 mL) was added, the mixture was washed 2× with 1N HCl and 1× with brine prior to drying over Na2SO4. Concentration of the solution and purification of the crude product by silical gel column gave intermediate AZ (286 mg).

Workup

  1. stirringAfter stirring overnight
  2. customthe reaction was quenched with a saturated solution of NaHCO3
  3. extractionThe mixture was extracted 3× with AcOEt
  4. washThe combined organic extracts were washed 1× with brine
  5. dry with materialto drying over Na2SO4
  6. customConcentration of the solution gave an oily residue, which
  7. stirringThe mixture was stirred for 2 h at room temperature
  8. washthe mixture was washed 2× with 1N HCl and 1× with brine
  9. dry with materialto drying over Na2SO4
  10. customConcentration of the solution and purification of the crude product by silical gel column
  11. customgave intermediate AZ (286 mg)

Sources & evidence

ORD record
ord-9dbd61893ac34467bd4262a1434c78ae
Source dataset
uspto-grants-2012_01
Patent number
US08106021B2

Reaction notes

Loading…