Ammonium formate → Tert-butyl 3-(2-(pyridin-3-yl)ethyl)piperazine-1-carboxylate

HRID 70133Notes

Reaction equation

HRID 70133 reaction equation
C([O-])=O.[NH4+].[N:5]1[CH:10]=[CH:9][CH:8]=[C:7]([CH2:11][CH2:12][CH:13]2[CH2:18][N:17]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:16][CH2:15][N:14]2C(OCC2C=CC=CC=2)=O)[CH:6]=1>CCO.[OH-].[OH-].[Pd+2]>[N:5]1[CH:10]=[CH:9][CH:8]=[C:7]([CH2:11][CH2:12][CH:13]2[NH:14][CH2:15][CH2:16][N:17]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:18]2)[CH:6]=1

Participants

5

Reactant 2

HCID 2723923Ammonium formateHCID 596715351-Benzyl 4-tert-butyl 2-(2-(pyridin-3-yl)ethyl)piperazine-1,4-dicarboxylate

Product 1

HCID 59671489Tert-butyl 3-(2-(pyridin-3-yl)ethyl)piperazine-1-carboxylateYield 60.1%

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 702EthanolSolvent

Procedure

Ammonium formate (0.492 g, 7.80 mmol) was added to a mixture of 1-benzyl 4-tert-butyl 2-(2-(pyridin-3-yl)ethyl)piperazine-1,4-dicarboxylate (1.66 g, 3.90 mmol) and palladium hydroxide on carbon (˜20% Pd, 0.137 g, 0.20 mmol) in EtOH (100 mL). The reaction mixture was heated to reflux for 3 h. Upon cooling to rt, the reaction mixture was filtered though Celite®, and the filtrate was concentrated under reduced pressure. Purification by column chomatography (0 to 5% MeOH in CH2Cl2 gradient) gave 0.683 g (60%) of the desired product. Rf=0.34 in 10% MeOH/CH2Cl2. LC-MS: RT=3.33 min., [M+H]+=292.2.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux for 3 h
  3. filtrationthe reaction mixture was filtered though Celite®
  4. concentrationthe filtrate was concentrated under reduced pressure
  5. customPurification by column chomatography (0 to 5% MeOH in CH2Cl2 gradient)

Sources & evidence

ORD record
ord-fc470aa0de9d43dfb1e767071e3055b4
Source dataset
uspto-grants-2014_09
Patent number
US08822472B2

Reaction notes

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