Dichloromethane → 5-bromo-3-(2-methoxy-phenyl)-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrrolo[2,3-b]pyridine

HRID 2234657Notes

Reaction equation

HRID 2234657 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:10](I)=[CH:9][N:8]([CH2:12][O:13][CH2:14][CH2:15][Si:16]([CH3:19])([CH3:18])[CH3:17])[C:5]2=[N:6][CH:7]=1.[CH3:20][O:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=1B(O)O.ClCCl.C(=O)([O-])[O-].[Na+].[Na+]>Cl[Pd]Cl.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].O1CCCC1.C(#N)C>[Br:1][C:2]1[CH:3]=[C:4]2[C:10]([C:23]3[CH:24]=[CH:25][CH:26]=[CH:27][C:22]=3[O:21][CH3:20])=[CH:9][N:8]([CH2:12][O:13][CH2:14][CH2:15][Si:16]([CH3:19])([CH3:18])[CH3:17])[C:5]2=[N:6][CH:7]=1

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 10340Sodium CarbonateHCID 27339582-Methoxyphenylboronic acidHCID 592970265-bromo-3-iodo-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrrolo[2,3-b]pyridine

Product 1

HCID 592970285-bromo-3-(2-methoxy-phenyl)-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrrolo[2,3-b]pyridineYield 70.1%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
65 °C

Procedure

Into a 50 ml round bottom pressure tube were added 5-bromo-3-iodo-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrrolo[2,3-b]pyridine (2.36 g, 5.2 mmol), 2-methoxyphenyl boronic acid (792 mg, 5.2 mmol), [1,1′-Bis(diphenylphosphino)-ferrocene]-dichloropalladium(II)-complex with dichlormethane (1:1) (43 mg, 0.052 mmol), acetonitrile (20 mL), tetrahydrofuran (5 ml) and of sodium carbonate (aq. 2 M, 9 ml, 18.0 mmol). The flask was sealed and heated at 65° C. for 2 hours. The reaction mixture was cooled to room temperature and concentrated. The residue was purified by flash chromatography (20% ethyl acetate in hexanes) to give 1.58 g (70%) of 5-bromo-3-(2-methoxy-phenyl)-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrrolo[2,3-b]pyridine. 1H-NMR (250 MHz, CDCl3) δ 8.355 (d, J=2.0 Hz, 1H), 8.155 (d, J=2 Hz, 1H), 7.64 (s, 1H), 7.50 (dd, J=7.5, 1.5 Hz, 1H), 7.23-7.35 (m, 1H), 6.98-7.10 (m, 2H), 5.68 (s, 2H), 3.86 (s, 3H), 3.58 (t, J=8.4 Hz, 2H), 0.94 (t, J=8.4 Hz, 3H), −0.06 (s, 9H); MS: m/z 432.1+434.1 (M+H+).

Workup

  1. customThe flask was sealed
  2. temperatureThe reaction mixture was cooled to room temperature
  3. concentrationconcentrated
  4. customThe residue was purified by flash chromatography (20% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-7c222a8c188440459de2201e1054e078
Source dataset
uspto-grants-2010_05
Patent number
US07709645B2

Reaction notes

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