2,3-Diaminopyridine → tert-Butyl 4-[(2-aminopyridin-3-yl)amino]piperidine-1-carboxylate

HRID 2378951Notes

Reaction equation

HRID 2378951 reaction equation
O=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1.[N:15]1[CH:20]=[CH:19][CH:18]=[C:17]([NH2:21])[C:16]=1[NH2:22].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCCl>[NH2:22][C:16]1[C:17]([NH:21][CH:2]2[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]2)=[CH:18][CH:19]=[CH:20][N:15]=1

Participants

5

Reactant 3

HCID 99562,3-DiaminopyridineHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 5049666Sodium triacetoxyborohydride2×

Product 1

HCID 22293217tert-Butyl 4-[(2-aminopyridin-3-yl)amino]piperidine-1-carboxylateYield 48%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

tert-Butyl 4-oxopiperidine-1-carboxylate (9.59 g, 48.1 mmol) and pyridine-2,3-diamine (5.0 g, 45.8 mmol) were combined and dissolved in 1,2-dichloroethane (75 ml). Sodium triacetoxyborohydride (14.5 g, 68.4 mmol) was added to the mixture. Reaction stirred at room temperature for 7 hours. Additional sodium triacetoxyborohydride (3.60 g, 16.99 mmol) was added to the mixture. Reaction stirred at room temperature for 18 hours. Reaction was quenched with 1N sodium hydroxide. Material was extracted twice with dichloromethane and the aqueous phase was discarded. Material was washed successively with 1N sodium hydroxide, water, and brine and the aqueous phases were discarded. Organics were dried MgSO4, filtered and then concentrated to dryness. Silica gel chromatography eluting methanol-dichloromethane afforded the title compound as tan foam in 48% yield. MS (M−H)−=291.2.

Workup

  1. customReaction
  2. customReaction
  3. stirringstirred at room temperature for 18 hours
  4. customReaction
  5. customwas quenched with 1N sodium hydroxide
  6. extractionMaterial was extracted twice with dichloromethane
  7. washMaterial was washed successively with 1N sodium hydroxide, water, and brine
  8. filtrationfiltered
  9. concentrationconcentrated to dryness
  10. washSilica gel chromatography eluting methanol-dichloromethane

Sources & evidence

ORD record
ord-a4f7a673fb9f4e5b9b22872ec131a5df
Source dataset
uspto-grants-2008_12
Patent number
US07470680B2

Reaction notes

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