4-Aminopyridine → HCID 58404912, compound

HRID 1253533Notes

Reaction equation

HRID 1253533 reaction equation
Br[C:2]1[CH:3]=[N:4][N:5]2[CH:10]=[C:9]([C:11]3[CH:12]=[N:13][N:14]([CH3:16])[CH:15]=3)[CH:8]=[C:7]([O:17][CH3:18])[C:6]=12.[NH2:19][C:20]1[CH:25]=[CH:24][N:23]=[CH:22][CH:21]=1.N12CCCN=C1CCCCC2.[O:37]1CCOC[CH2:38]1>[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[Mo].CC1C(P(C2C([CH2-])=CC=CC=2)C2C(C)=CC=CC=2)=CC=CC=1.CC1C(P(C2C([CH2-])=CC=CC=2)C2C(C)=CC=CC=2)=CC=CC=1.CC(O)=O.CC(O)=O.[Pd].[Pd]>[CH3:18][O:17][C:7]1[C:6]2[N:5]([N:4]=[CH:3][C:2]=2[C:38]([NH:19][C:20]2[CH:25]=[CH:24][N:23]=[CH:22][CH:21]=2)=[O:37])[CH:10]=[C:9]([C:11]2[CH:12]=[N:13][N:14]([CH3:16])[CH:15]=2)[CH:8]=1

Participants

7

Reactant 4

HCID 17274-AminopyridineHCID 312751,4-DioxaneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 58404689HCID 58404689, compound

Product 1

HCID 58404912HCID 58404912, compound

Reagents, catalysts & solvents 2

HCID 98885Molybdenum carbonyl (Mo(CO)6)CatalystHCID 11104995trans-Bis(acetato)bis[2-[bis(2-methylphenyl)phosphino]benzyl]dipalladium(II)Catalyst

Conditions

Temperature
100 °C

Procedure

3-bromo-4-methoxy-6-(1-methyl-1H-pyrazol-4-yl)pyrazolo[1,5-a]pyridine (30 mg, 0.098 mmol), 4-aminopyridine (18 mg, 0.20 mmol), 1,8-diazabicyclo[5.4.0]undec-7-ene (0.059 ml, 0.39 mmol), molybdenum hexacarbonyl (0.013 ml, 0.098 mmol), tri-(tert-butyl)phosphonium hydrogen tetrafluoroborate salt (3.0 mg, 0.01 mmol), trans-di-mu-acetatobis[2-(di-o-tolylphosphino)benzyl]dipalladium (II) (4.6 mg, 0.0049 mmol) were added to dioxane (3.9 ml). The mixture was sparged with argon for 3 minutes and heated to 100° C. After 16 h, the reaction mixture was cooled and purified directly by preparative HPLC Reverse phase (C-18), eluting with acetonitrile/water+0.05% TFA to give 4-methoxy-6-(1-methyl-1H-pyrazol-4-yl)-N-pyridin-4-ylpyrazolo[1,5-a]pyridine-3-carboxamide. 1H NMR (500 MHz, DMSO-d6) δ 10.30 (s, 1H); 8.81 (s, 1H); 8.44 (d, 2H); 8.37 (d, 2H); 8.09 (s, 1H); 7.67 (d, 2H); 7.24 (s, 1H); 4.10 (s, 3H); 3.88 (s, 3H). LRMS (ESI) calculated for C18H17N6O2 [M+H]+, 349.1 found 349.0.

Workup

  1. customThe mixture was sparged with argon for 3 minutes
  2. temperaturethe reaction mixture was cooled
  3. custompurified directly by preparative HPLC Reverse phase (C-18)
  4. washeluting with acetonitrile/water+0.05% TFA

Sources & evidence

ORD record
ord-21df39f9987f44c0bb950e5f57aea999
Source dataset
uspto-grants-2013_06
Patent number
US08455477B2

Reaction notes

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