Diethyl Ether → 1-Benzenesulfonyl-4-tributylstannanyl-1H-pyrrolo[2,3-c]pyridine

HRID 1945583Notes

Reaction equation

HRID 1945583 reaction equation
[C:1]1([S:7]([N:10]2[C:14]3=[CH:15][N:16]=[CH:17][C:18](Br)=[C:13]3[CH:12]=[CH:11]2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C(OCC)C.C([Li])CCC.[CH2:30]([Sn:34](Cl)([CH2:39][CH2:40][CH2:41][CH3:42])[CH2:35][CH2:36][CH2:37][CH3:38])[CH2:31][CH2:32][CH3:33]>C1COCC1.C1CCCCC1>[C:1]1([S:7]([N:10]2[C:14]3=[CH:15][N:16]=[CH:17][C:18]([Sn:34]([CH2:35][CH2:36][CH2:37][CH3:38])([CH2:39][CH2:40][CH2:41][CH3:42])[CH2:30][CH2:31][CH2:32][CH3:33])=[C:13]3[CH:12]=[CH:11]2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 15096Tributyltin ChlorideHCID 583564464-bromo-1-(phenylsulfonyl)-1H-pyrrolo[2,3-c]pyridineHCID 178418339Butyllithium

Product 1

HCID 596055161-Benzenesulfonyl-4-tributylstannanyl-1H-pyrrolo[2,3-c]pyridine

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8078CyclohexaneSolvent

Conditions

Temperature
-78 °C

Procedure

1-Benzenesulfonyl-4-bromo-1H-pyrrolo[2,3-c]pyridine (0.34 g, 1.0 mmol) was dissolved in THF (5 mL) and diethyl ether (5 mL) and the solution cooled to −78° C. n-Butyllithium (0.756 M in hexanes, 1.2 mL, 5.0 mmol) was added over 5 min then the mixture was stirred for 15 min before addition of tributyltin chloride (0.39 g, 1.2 mmol) over 10 min. The reaction mixture was stirred at −78° C. for 1 hour then allowed to warm to room temperature and diluted with cyclohexane (50 mL). The reaction mixture was washed with water (3×30 mL) followed by brine, before the organic phase was dried (MgSO4) and evaporated. The crude residue was purified by chromatography on alumina using 30% EtOAc in cyclohexane. The material was further purified by flash chromatography (Si—PPC), eluting with 5-10% EtOAc in cyclohexane to yield the title product. 1H NMR (CDCl3, 300 MHz): δ 9.23 (s, 1H), 8.36 (s, 1H), 7.91-8.00 (m, 2H), 7.71, d, J=1.1 Hz, 1H), 7.55-7.63 (m, 1H), 7.42-7.53 (m, 2H), 6.59 (d, J=1.1 Hz, 1H), 1.45-1.65 (m, 6H), 1.21-1.38 (m, 6H), 1.09-1.20 (m, 6H), 0.85 (t, J=7.5 Hz, 9H).

Workup

  1. additionwas added over 5 min
  2. temperatureto warm to room temperature
  3. washThe reaction mixture was washed with water (3×30 mL)
  4. dry with materialwas dried (MgSO4)
  5. customevaporated
  6. customThe crude residue was purified by chromatography on alumina using 30% EtOAc in cyclohexane
  7. customThe material was further purified by flash chromatography (Si—PPC)
  8. washeluting with 5-10% EtOAc in cyclohexane

Sources & evidence

ORD record
ord-e4f3b23c6244462eaf6568c3828d7f46
Source dataset
uspto-grants-2013_03
Patent number
US08394796B2

Reaction notes

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