HCID 60168011, compound → HCID 71678738, compound

HRID 60409Notes

Reaction equation

HRID 60409 reaction equation
[C:1]([O:4][C:5]1[C:6]([CH3:25])=[C:7]2[CH2:23][CH2:22][N:21]([CH3:24])[C:8]2=[N:9][C:10]=1[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20])(=[O:3])[CH3:2]>C1C=CC=CC=1.[O-2].[O-2].[O-2].[Ni+3].[Ni+3]>[C:1]([O:4][C:5]1[C:6]([CH3:25])=[C:7]2[CH:23]=[CH:22][N:21]([CH3:24])[C:8]2=[N:9][C:10]=1[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20])(=[O:3])[CH3:2]

Participants

4

Reactant 1

HCID 60168011HCID 60168011, compound

Product 1

HCID 71678738HCID 71678738, compound

Reagents, catalysts & solvents 2

HCID 10313272Nickel oxide (Ni2O3)CatalystHCID 241BenzeneSolvent

Procedure

To a solution containing 51 mg (0.15 mmol) of 2b in 4 mL of benzene was added 42 mg (0.46 mmol) of nickel peroxide. The reaction was stirred at reflux for 18 h. The reaction mixture was filtered through a silica gel plug and washed with three 20-mL portions of benzene, followed by two 20-mL portions of ethyl acetate. The combined organic layer was washed with brine, dried over anhydrous MgSO4, filtered, and concentrated under diminished pressure. The residue was purified via flash chromatography on a silica gel column (27×1.7 cm). Step gradient elution with 1:10→1:4 ethyl acetate-hexanes as eluent gave 6-decyl-1,4-dimethyl-1H-pyrrolo[2,3-b]pyridin-5-yl acetate (2e) as a colorless oil: yield 50 mg (48%); silica gel TLC Rf 0.35 (3:7 ethyl acetate-hexanes); 1H NMR (CDCl3) δ 1.05 (t, 3H, J=7.2 Hz), 1.39-1.52 (m, 14H), 1.76 (quint, 2H, J=8.0 Hz), 2.17 (s, 3H), 2.43 (s, 3H), 2.58 (t, 2H, J=8.0 Hz), 3.41 (s, 3H), 6.27 (d, 1H, J=3.6 Hz), 6.92 (d, 1H, J=3.6 Hz).

Workup

  1. temperatureat reflux for 18 h
  2. filtrationThe reaction mixture was filtered through a silica gel plug
  3. washwashed with three 20-mL portions of benzene
  4. washThe combined organic layer was washed with brine
  5. dry with materialdried over anhydrous MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated under diminished pressure
  8. customThe residue was purified via flash chromatography on a silica gel column (27×1.7 cm)
  9. washStep gradient elution with 1:10→1:4 ethyl acetate-hexanes as eluent

Sources & evidence

ORD record
ord-ddb50ac0a87f48bcb926304f175fa7be
Source dataset
uspto-grants-2016_09
Patent number
US09440967B2

Reaction notes

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