ethyl 5-(1-isopropyl-1H-pyrazol-5-yl)-3,6-dihydro-2H-pyran-4-carboxylate → (+/-) (3S,4R)-ethyl 3-(1-isopropyl-1H-pyrazol-5-yl)tetrahydro-2H-pyran-4-carboxylate

HRID 1770792Notes

Reaction equation

HRID 1770792 reaction equation
[CH:1]([N:4]1[C:8]([C:9]2[CH2:14][O:13][CH2:12][CH2:11][C:10]=2[C:15]([O:17][CH2:18][CH3:19])=[O:16])=[CH:7][CH:6]=[N:5]1)([CH3:3])[CH3:2]>CCO.O.C(Cl)(Cl)Cl.[Pd]>[CH:1]([N:4]1[C:8]([C@@H:9]2[C@H:10]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH2:11][CH2:12][O:13][CH2:14]2)=[CH:7][CH:6]=[N:5]1)([CH3:3])[CH3:2]

Participants

6

Reactant 1

HCID 90409040ethyl 5-(1-isopropyl-1H-pyrazol-5-yl)-3,6-dihydro-2H-pyran-4-carboxylate

Product 1

HCID 90444162(+/-) (3S,4R)-ethyl 3-(1-isopropyl-1H-pyrazol-5-yl)tetrahydro-2H-pyran-4-carboxylateYield 69.2%

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalyst2×HCID 702EthanolSolvent2×HCID 962WaterSolventHCID 6212ChloroformSolvent

Procedure

To a solution of ethyl 5-(1-isopropyl-1H-pyrazol-5-yl)-3,6-dihydro-2H-pyran-4-carboxylate (100 mg, 0.38 mmol) in EtOH (2 mL) was added Pd/C (50 mg), then it was charged with H2 (1 atm) and stirred at room temperature for 3 days, Mass spec shows about 50% conversion. The mixture was then added a solution of NH4CO2H (200 mg) in water (2 ml) and additional Pd/C, and the mixture was further heated at 75° C. for 1.5 h, after cooled to room temperature, the reaction was diluted with EtOH, pd/C was filtered off, and the filtrate was concentrated to give crude oil, which was diluted with CHCl3, organic layer was washed with Sat. NaHCO3, dried and concentrated to give crude product, which was purified by column (Hexanes/EtOAc=65:35) to give (±)ethyl(3S,4R)-3-(1-isopropyl-1H-pyrazol-5-yl)tetrahydro-2H-pyran-4-carboxylate (70 mg).

Workup

  1. additionit was charged with H2 (1 atm)
  2. temperatureafter cooled to room temperature
  3. filtrationpd/C was filtered off
  4. concentrationthe filtrate was concentrated
  5. customto give crude oil, which
  6. washwas washed with Sat. NaHCO3
  7. customdried
  8. concentrationconcentrated
  9. customto give crude product, which
  10. customwas purified by column (Hexanes/EtOAc=65:35)

Sources & evidence

ORD record
ord-30162b37159843a49264277900e90709
Source dataset
uspto-grants-2016_02
Patent number
US09248199B2

Reaction notes

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