Dimethylformamide → (+/-)-tert-butyl 1-(1-methoxy-1-oxopropan-2-yl)-2-methyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylate

HRID 2206565Notes

Reaction equation

HRID 2206565 reaction equation
[CH3:1][C:2]1[NH:10][C:5]2=[N:6][CH:7]=[CH:8][CH:9]=[C:4]2[C:3]=1[C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12].C(=O)([O-])[O-].[Cs+].[Cs+].CN(C=O)C.Br[CH:30]([CH3:35])[C:31]([O:33][CH3:34])=[O:32]>[Cl-].[Na+].O>[CH3:34][O:33][C:31](=[O:32])[CH:30]([N:10]1[C:5]2=[N:6][CH:7]=[CH:8][CH:9]=[C:4]2[C:3]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])=[C:2]1[CH3:1])[CH3:35]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 10796Cesium carbonateHCID 95576Methyl 2-bromopropionateHCID 89739113tert-Butyl 2-methyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylate

Product 1

HCID 117779095(+/-)-tert-butyl 1-(1-methoxy-1-oxopropan-2-yl)-2-methyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylateYield 64%

Reagents, catalysts & solvents 1

HCID 57417360Sodium chloride; waterSolvent

Procedure

To a pyrex vial was added tert-butyl 2-methyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylate (2.491 g, 10.72 mmol) and cesium carbonate (4.54 g, 13.94 mmol). The atmosphere in the vial was vac/purged 3× with N2 then DMF (24 mL) and methyl 2-bromopropanoate (2.393 ml, 21.45 mmol) were added. The reaction was mixed at ambient temperature overnight. The reaction was poured into half-saturated brine and extracted with EtOAc. The combined organic layer was washed 1× each with water then brine, dried over Na2SO4, filtered, deposited onto silica gel and purified by CC (Biotage, 100 g column) using 25% EtOAc in Hex (6 CV) then 50% (6 CV) as eluent to provide (±)-tert-butyl 1-(1-methoxy-1-oxopropan-2-yl)-2-methyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylate (2.132 g, 64%). LRMS (M+H+) m/z: calcd 319.37. found 319.2.

Workup

  1. customThe atmosphere in the vial was vac/purged 3× with N2
  2. additionThe reaction was mixed at ambient temperature overnight
  3. extractionextracted with EtOAc
  4. washThe combined organic layer was washed 1× each with water
  5. dry with materialbrine, dried over Na2SO4
  6. filtrationfiltered
  7. custompurified by CC (Biotage, 100 g column)

Sources & evidence

ORD record
ord-3c4c9a326c304fe5a51f1ddf88f95c8f
Source dataset
uspto-grants-2016_06
Patent number
US09371331B2

Reaction notes

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