Acetic Acid → tert-Butyl 9-(5,6-dihydro-[1,2,4]triazolo[1,5-a]pyrazin-7(8H)-yl)-3-azaspiro[5.5]undecane-3-carboxylate

HRID 1253708Notes

Reaction equation

HRID 1253708 reaction equation
C(O)(=O)C.O=[C:6]1[CH2:23][CH2:22][C:9]2([CH2:14][CH2:13][N:12]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:11][CH2:10]2)[CH2:8][CH2:7]1.[N:24]1[CH:25]=[N:26][N:27]2[CH2:32][CH2:31][NH:30][CH2:29][C:28]=12.[Na]>C(Cl)Cl.C([O-])(O)=O.[Na+]>[N:24]1[CH:25]=[N:26][N:27]2[CH2:32][CH2:31][N:30]([CH:6]3[CH2:23][CH2:22][C:9]4([CH2:14][CH2:13][N:12]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:11][CH2:10]4)[CH2:8][CH2:7]3)[CH2:29][C:28]=12

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 5360545SodiumHCID 184069195H,6H,7H,8H-(1,2,4)triazolo(1,5-a)pyrazineHCID 51072194tert-Butyl 9-oxo-3-azaspiro[5.5]undecane-3-carboxylate

Product 1

HCID 66701117tert-Butyl 9-(5,6-dihydro-[1,2,4]triazolo[1,5-a]pyrazin-7(8H)-yl)-3-azaspiro[5.5]undecane-3-carboxylateYield 62%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 516892Sodium BicarbonateSolvent

Procedure

Acetic acid (2.34 eq.) was added to a solution of tert-butyl 9-oxo-3-azaspiro[5.5]undecane-3-carboxylate (1.122 mmol, 1 eq.) and 5,6,7,8-tetrahydro-[1,2,4]triazolo[1,5-a]pyrazine (1.14 eq.) in methylene chloride (7 ml). Sodium triacetoxyborhydride (1.4 eq) was then added and the mixture was stirred at room temperature overnight. The reaction mixture was diluted with methylene chloride and sat. NaHCO3 solution. The aqueous phase was washed with methylene chloride (2×20 ml), and the combined organic phases were dried over Na2SO4 and concentrated in vacuo. The crude product was purified by column chromatography (silica, ethyl acetate/ethanol 10:1) to obtain the desired product. Yield: 62%

Workup

  1. washThe aqueous phase was washed with methylene chloride (2×20 ml)
  2. dry with materialthe combined organic phases were dried over Na2SO4
  3. concentrationconcentrated in vacuo
  4. customThe crude product was purified by column chromatography (silica, ethyl acetate/ethanol 10:1)

Sources & evidence

ORD record
ord-14a9f0001dd04364973ca7fee12507fb
Source dataset
uspto-grants-2013_06
Patent number
US08455475B2

Reaction notes

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