Ammonium formate → (2,2-dimethyl-1,3-dioxolan-4-yl)methyl-1H-indol-5-amine

HRID 1404013Notes

Reaction equation

HRID 1404013 reaction equation
C([C:5]1[N:6]([CH2:17][C@@H:18]2[CH2:22][O:21][C:20]([CH3:24])([CH3:23])[O:19]2)[C:7]2[C:12]([CH:13]=1)=[CH:11][C:10]([N+:14]([O-])=O)=[CH:9][CH:8]=2)(C)(C)C.C([O-])=O.[NH4+]>C(O)C.O.[Pd]>[CH3:23][C:20]1([CH3:24])[O:19][CH:18]([CH2:17][N:6]2[C:7]3[C:12](=[CH:11][C:10]([NH2:14])=[CH:9][CH:8]=3)[CH:13]=[CH:5]2)[CH2:22][O:21]1

Participants

6

Reactant 2

HCID 2723923Ammonium formateHCID 59129186(R)-2-tert-butyl-((2,2-dimethyl-1,3-dioxolan-4-yl)methyl)-5-nitro-1H-indole

Product 1

HCID 69909767(2,2-dimethyl-1,3-dioxolan-4-yl)methyl-1H-indol-5-amineYield 120.4%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

To a stirred solution of (R)-2-tert-butyl-1-((2,2-dimethyl-1,3-dioxolan-4-yl)methyl)-5-nitro-1H-indole (1.0 g, 3.0 mmol) in ethanol (20 mL) and water (5 mL) was added ammonium formate (0.76 g, 12 mmol) followed by slow addition of 10% palladium on carbon (0.4 g). The mixture was stirred at room temperature for 1 h. The reaction mixture was filtered through a plug of celite and rinsed with ethyl acetate. The filtrate was evaporated under reduced pressure and the crude product was dissolved in ethyl acetate. The organic layer was washed with water (2×5 mL) and brine (2×5 mL). The organic layer was dried over Na2SO4, filtered and evaporated under reduced pressure to give (R)-2-tert-butyl-1-((2,2-dimethyl-1,3-dioxolan-4-yl)methyl-1H-indol-5-amine (0.89 g, 98%). 1H NMR (400 MHz, CDCl3) δ 7.04 (d, J=4 Hz, 1H), 6.70 (d, J=2.2 Hz, 1H), 6.48 (dd, J=2.2, 8.6 Hz, 1H), 6.05 (s, 1H), 4.38-4.1 (m, 2H), 4.21 (dd, J=7.5, 16.5 Hz, 1H), 3.87 (dd, J=6.0, 8.6 Hz, 1H), 3.66 (dd, J=6.0, 8.6 Hz, 1H), 3.33 (br s, 2H), 1.40 (s, 3H), 1.34 (s, 9H), 1.25 (s, 3H).

Workup

  1. filtrationThe reaction mixture was filtered through a plug of celite
  2. washrinsed with ethyl acetate
  3. customThe filtrate was evaporated under reduced pressure
  4. dissolutionthe crude product was dissolved in ethyl acetate
  5. washThe organic layer was washed with water (2×5 mL) and brine (2×5 mL)
  6. dry with materialThe organic layer was dried over Na2SO4
  7. filtrationfiltered
  8. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-ad6e74270bec42ae92d6078121ec85d7
Source dataset
uspto-grants-2014_12
Patent number
US08912199B2

Reaction notes

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