1,4-Dioxane → 1H-Pyrrolo[2,3-b]pyridine, 6-bromo-1-[tris(1-methylethyl)silyl]-

HRID 1025619Notes

Reaction equation

HRID 1025619 reaction equation
[Br:1][C:2]1[N:7]=[C:6]2[NH:8][CH:9]=[CH:10][C:5]2=[CH:4][CH:3]=1.[Si:11](OS(C(F)(F)F)(=O)=O)([CH:18]([CH3:20])[CH3:19])([CH:15]([CH3:17])[CH3:16])[CH:12]([CH3:14])[CH3:13].CCN(C(C)C)C(C)C.O1CCOCC1>CCOC(C)=O>[Br:1][C:2]1[N:7]=[C:6]2[N:8]([Si:11]([CH:18]([CH3:20])[CH3:19])([CH:15]([CH3:17])[CH3:16])[CH:12]([CH3:14])[CH3:13])[CH:9]=[CH:10][C:5]2=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 312751,4-DioxaneHCID 81531DiisopropylethylamineHCID 2724529Triisopropylsilyl trifluoromethanesulfonateHCID 111599156-Bromo-7-azaindole

Product 1

HCID 580876901H-Pyrrolo[2,3-b]pyridine, 6-bromo-1-[tris(1-methylethyl)silyl]-Yield 85%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
55 °C

Procedure

In a 25 mL round-bottomed flask, 6-bromo-1H-pyrrolo[2,3-b]pyridine (250 mg, 1.27 mmol, Eq: 1.00), TIPS-OTf (972 mg, 860 μl, 3.17 mmol, Eq: 2.5) and DIEA (492 mg, 665 μl, 3.81 mmol, Eq: 3) were combined with dioxane (6.25 ml) to give a light brown solution. The reaction mixture was heated to 55° C. and stirred for 16 h. The reaction mixture was poured into 20 mL EtOAc and extracted with sat NaHCO3 (3×10 mL). The organic layers were dried over MgSO4 and concentrated in vacuo. The crude material was purified by flash chromatography (silica gel, 12 g, 5% to 10% EtOAc in hexanes) to give 6-bromo-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine (380 mg, 85%) of colorless oil.

Workup

  1. customto give a light brown solution
  2. extractionextracted with sat NaHCO3 (3×10 mL)
  3. dry with materialThe organic layers were dried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customThe crude material was purified by flash chromatography (silica gel, 12 g, 5% to 10% EtOAc in hexanes)

Sources & evidence

ORD record
ord-4acb1e8677524ff8b6f8acc0a9d8f39b
Source dataset
uspto-grants-2014_05
Patent number
US08729078B2

Reaction notes

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