Dimethylformamide → tert-Butyl 4-bromo-1H-pyrrolo[2,3-b]pyridine-1-carboxylate

HRID 2361233Notes

Reaction equation

[Br:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[NH:8][CH:9]=[CH:10][C:3]=12.FC(S(OS(C(F)(F)F)(=O)=O)(=O)=[O:16])(F)F.N1[C:30]2=[N+]([O-])C=C[CH:34]=[C:29]2[CH:28]=C1.CN(C)[CH:38]=[O:39]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC>[Br:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[N:8]([C:38]([O:39][C:29]([CH3:30])([CH3:34])[CH3:28])=[O:16])[CH:9]=[CH:10][C:3]=12

Participants

Conditions

Temperature: 0 °C

Procedure

4-Bromo-1H-pyrrolo[2,3-b]pyridine. A solution of trifluoromethyl sulfonic anhydride (9.3 g, 33 mmol) was added dropwise to a mixture of 1H-pyrrolo[2,3-b]pyridine 7-oxide (3 g, 22 mmol) and tetrabutyl ammonium bromide (10.8 g, 33 mmol) in N,N-dimethylformamide (30 mL) at 0° C. The resulting mixture was stirred at 0° C. for 4 h and at room temperature overnight. The reaction was quenched with water and neutralized with 1N sodium hydroxide to pH=7. The resulting mixture was extracted twice with a mixture of methylene chloride and i-propanol (30 mL, Vm:Vp=4:1). The organic layer was combined, dried over anhydrous sodium sulfate, concentrated and purified by a reverse-phase preparatory HPLC (0-30%: acetonitrile+0.1% TFA in water+0.1% TFA, over 15 min.) to give the title compound (1.5 g, 34.3% yield). MS(ESI) m/z 196.8 [M+1]+, 198.8 [M+3]+.

Workup

customThe reaction was quenched with water and neutralized with 1N sodium hydroxide to pH=7
extractionThe resulting mixture was extracted twice with a mixture of methylene chloride and i-propanol (30 mL, Vm:Vp=4:1)
dry with materialdried over anhydrous sodium sulfate
concentrationconcentrated
custompurified by a reverse-phase preparatory HPLC (0-30%: acetonitrile+0.1% TFA in water+0.1% TFA, over 15 min.)

Sources & evidence

ORD record: ord-4d205d0a96834e92b634ab9684f8131f
Source dataset: uspto-grants-2014_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08686135B2

Reaction notes

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