Ammonium formate → Tert-butyl 2-((pyridin-3-yloxy)methyl)piperazine-1-carboxylate

HRID 70201Notes

Reaction equation

HRID 70201 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([O:7][CH2:8][CH:9]2[CH2:14][N:13](C(OCC3C=CC=CC=3)=O)[CH2:12][CH2:11][N:10]2[C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH:2]=1.C([O-])=O.[NH4+]>CCO.CCOC(C)=O.[OH-].[OH-].[Pd+2]>[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([O:7][CH2:8][CH:9]2[CH2:14][NH:13][CH2:12][CH2:11][N:10]2[C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH:2]=1

Participants

6

Reactant 2

HCID 2723923Ammonium formateHCID 596716061-Tert-butyl 4-benzyl 2-((pyridin-3-yloxy)methyl)piperazine-1,4-dicarboxylate

Product 1

HCID 59671473Tert-butyl 2-((pyridin-3-yloxy)methyl)piperazine-1-carboxylateYield 87.1%

Reagents, catalysts & solvents 3

HCID 9942167Palladium hydroxideCatalystHCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

Palladium hydroxide on carbon (˜40% palladium, 0.170 g, 0.12 mmol) was added to a solution of 1-tert-butyl 4-benzyl 2-((pyridin-3-yloxy)methyl)piperazine-1,4-dicarboxylate (0.649 g, 1.52 mmol) and ammonium formate (0.191 g, 3.03 mmol) in EtOH (10 mL), and the reaction mixture was heated to 80° C. for 2 h. Upon cooling to rt, the reaction mixture was diluted with EtOAc (40 mL) and washed with water (3×30 mL) and brine (30 mL). The organics were dried over Na2SO4, filtered, and concentrated under reduced pressure, yielding 388.4 mg (87%) of the desired product as a white, waxy solid. LC-MS: RT=3.90 min, [M+H]+=294.1.

Workup

  1. temperatureUpon cooling to rt
  2. washwashed with water (3×30 mL) and brine (30 mL)
  3. dry with materialThe organics were dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-68f5d6a81e6b46de9ec8733c8f0b32b4
Source dataset
uspto-grants-2014_09
Patent number
US08822472B2

Reaction notes

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