Ammonium formate → HCID 70872875, compound

HRID 712997Notes

Reaction equation

HRID 712997 reaction equation
[C:1]([N:5]1[CH2:10][C:9]2([CH2:15][CH2:14][N:13]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:12][CH2:11]2)[O:8][CH:7]([CH:23]=[CH2:24])[CH2:6]1)([CH3:4])([CH3:3])[CH3:2].C([O-])=O.[NH4+]>CO.[OH-].[OH-].[Pd+2]>[C:1]([N:5]1[CH2:6][CH:7]([CH2:23][CH3:24])[O:8][C:9]2([CH2:15][CH2:14][N:13]([C:16]([O:18][C:19]([CH3:21])([CH3:20])[CH3:22])=[O:17])[CH2:12][CH2:11]2)[CH2:10]1)([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 2

HCID 2723923Ammonium formateHCID 68291485HCID 68291485, compound

Product 1

HCID 70872875HCID 70872875, compoundYield 96.3%

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 887MethanolSolvent

Conditions

Temperature
55 °C

Procedure

To a solution of tert-butyl 4-tert-butyl-2-vinyl-1-oxa-4,9-diazaspiro[5.5]undecane-9-carboxylate (550 mg, 1.62 mmol) in methanol (10 mL) was added Pd(OH)2 (447 mg, 3.18 mmol) and ammonium formate (2.19 g, 34.7 mmol) and the reaction mixture heated at 55° C. for 20 min. The reaction mixture was filtered, concentrated to −10 mL and then diluted with dichloromethane and 1:1 saturated NaHCO3 solution/1M NaOH. The dichloromethane layer was separated and the aqueous layer extracted with dichloromethane (5×20 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo to provide tert-butyl 8-tert-butyl-10-ethyl-11-oxa-3,8-diazaspiro[5.5]undecane-3-carboxylate (530 mg, 1.56 mmol, 96%) as a colorless oil. ESI-MS m/z calc. 340.3. found 341.3 (M+1)+; Retention time: 1.16 minutes (3 min run). 1H NMR (400 MHz, DMSO-d6) δ 3.59 (t, J=11.7 Hz, 2H), 3.48-3.36 (m, 1H), 3.11 (br s, 1H), 2.91 (br s, 1H), 2.80 (d, J=10.7 Hz, 1H), 2.71 (dd, J=11.1, 1.7 Hz, 1H), 2.23 (d, J=14.0 Hz, 1H), 1.81 (d, J=11.1 Hz, 1H), 1.71 (t, J=10.6 Hz, 1H), 1.39 (s, 9H), 1.38-1.22 (m, 5H), 0.96 (s, 9H), 0.89 (t, J=7.4 Hz, 3H).

Workup

  1. filtrationThe reaction mixture was filtered
  2. concentrationconcentrated to −10 mL
  3. additiondiluted with dichloromethane and 1:1 saturated NaHCO3 solution/1M NaOH
  4. customThe dichloromethane layer was separated
  5. extractionthe aqueous layer extracted with dichloromethane (5×20 mL)
  6. dry with materialThe combined organic layers were dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-3d48723fd5644515bc079261f92345a0
Source dataset
uspto-grants-2015_11
Patent number
US09181273B2

Reaction notes

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