2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 1H-Pyrrolo[2,3-B]pyridine-5-carboxaldehyde, 1-[(1,1-dimethylethyl)dimethylsilyl]-

HRID 1994195Notes

Reaction equation

HRID 1994195 reaction equation
[C:1]([Si:5]([CH3:18])([CH3:17])[N:6]1[C:10]2=[N:11][CH:12]=[C:13]([CH:15]=[O:16])[CH:14]=[C:9]2[CH2:8][CH2:7]1)([CH3:4])([CH3:3])[CH3:2].C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>C(Cl)Cl.P([O-])([O-])([O-])=O>[C:1]([Si:5]([CH3:18])([CH3:17])[N:6]1[C:10]2=[N:11][CH:12]=[C:13]([CH:15]=[O:16])[CH:14]=[C:9]2[CH:8]=[CH:7]1)([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 587309341-(tert-Butyl-dimethyl-silanyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine-5-carbaldehyde

Product 1

HCID 497590381H-Pyrrolo[2,3-B]pyridine-5-carboxaldehyde, 1-[(1,1-dimethylethyl)dimethylsilyl]-Yield 21.1%

Reagents, catalysts & solvents 2

HCID 1061PhosphateSolventHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of the alcohol 13 (54 mg, 0.20 mmol) in a mixture of CH2Cl2 (15 mL) and 0.2 M pH 7 phosphate buffer (0.15 mL) was added DDQ (53 mg, 0.23 mmol) in three equal portions. When TLC analysis showed complete consumption of the starting material, the mixture was diluted with saturated aqueous NaHCO3 (16 mL) and stirred vigorously for 1 h. The mixture was then extracted with AcOEt (2×). The combined organic solutions were washed with saturated brine (1×), dried (MgSO4) and concentrated. The residue was purified by PTLC with benzene as eluent to afford aldehyde 16 (11 mg, 21%). 1H NMR (400 MHz; CDCl3) δ 0.66 (s, 6H), 0.94 (s, 9H), 6.67 (d, J=3.5 Hz, 1H), 7.34 (d, J=3.5 Hz, 1H), 8.37 (d, J=2.0 Hz, 1H), 8.76 (d, J=2.0 Hz, 1H), 10.11 (s, 1H).

Workup

  1. customconsumption of the starting material
  2. additionthe mixture was diluted with saturated aqueous NaHCO3 (16 mL)
  3. extractionThe mixture was then extracted with AcOEt (2×)
  4. washThe combined organic solutions were washed with saturated brine (1×)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. customThe residue was purified by PTLC with benzene as eluent

Sources & evidence

ORD record
ord-7c47729854e84166a95217da17562829
Source dataset
uspto-grants-2010_01
Patent number
US07652137B2

Reaction notes

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