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

HRID 1847839Notes

Reaction equation

HRID 1847839 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-c47a2cda2fb6427b8d6efb55740ad194
Source dataset
uspto-grants-2015_02
Patent number
US08952049B2

Reaction notes

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