Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1) → 5-methoxy-N-(2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-pyrrolo[3,2-b]pyridine-2-carboxamide

HRID 245713Notes

Reaction equation

HRID 245713 reaction equation
[CH3:1][O:2][C:3]1[N:8]=[C:7]2[CH:9]=[C:10]([C:12]([OH:14])=O)[NH:11][C:6]2=[CH:5][CH:4]=1.F[P-](F)(F)(F)(F)F.N1(OC(N(C)C)=[N+](C)C)C2N=CC=CC=2N=N1.[NH2:39][C:40]1[CH:45]=[CH:44][C:43]([B:46]2[O:54][C:51]([CH3:53])([CH3:52])[C:48]([CH3:50])([CH3:49])[O:47]2)=[CH:42][C:41]=1[O:55][CH3:56]>ClCCl.N1C=CC=CC=1>[CH3:1][O:2][C:3]1[N:8]=[C:7]2[CH:9]=[C:10]([C:12]([NH:39][C:40]3[CH:45]=[CH:44][C:43]([B:46]4[O:47][C:48]([CH3:49])([CH3:50])[C:51]([CH3:53])([CH3:52])[O:54]4)=[CH:42][C:41]=3[O:55][CH3:56])=[O:14])[NH:11][C:6]2=[CH:5][CH:4]=1

Participants

6

Reactant 3

HCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 177502072-Methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anilineHCID 177504105-Methoxy-1H-pyrrolo(3,2-b)pyridine-2-carboxylic acid

Product 1

HCID 673638075-methoxy-N-(2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-pyrrolo[3,2-b]pyridine-2-carboxamideYield 109.1%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6344DichloromethaneSolvent

Procedure

5-Methoxy-1 h-pyrrolo[3,2-b]pyridine-2-carboxylic acid (0.602 mmol, 116 mg) and O-(7-azabenzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (0.662 mmol, 252 mg) were added to a solution of 4-amino-3-methoxyphenylboronic acid pinacol ester (0.602 mmol, 150 mg) in dichloromethane (2.5 ml) and pyridine (0.5 ml) at 0° C. After stirring the reaction mixture overnight at room temperature it was concentrated in vacuo. Dichloromethane and water were added to the residue, the organic layer separated and washed with water. Both aqueous layers were extracted with dichloromethane. The combined organic layers were dried (sodium sulfate) and concentrated in vacuo. The residue was purified by column chromatography (silica gel, dichloromethane) to give 5-methoxy-N-(2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-pyrrolo[3,2-b]pyridine-2-carboxamide (278 mg).

Workup

  1. concentrationwas concentrated in vacuo
  2. additionDichloromethane and water were added to the residue
  3. customthe organic layer separated
  4. washwashed with water
  5. extractionBoth aqueous layers were extracted with dichloromethane
  6. dry with materialThe combined organic layers were dried (sodium sulfate)
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by column chromatography (silica gel, dichloromethane)

Sources & evidence

ORD record
ord-2ce1906485514bbd9a44a70f2cdc82c2
Source dataset
uspto-grants-2014_02
Patent number
US08658794B2

Reaction notes

Loading…