Water → 6-{4-[(Dimethylamino)sulfonyl]phenyl}-N-[(4,6-dimethyl-2-oxo-1,2-dihydro-3-pyridinyl)methyl]-1-(1-methylethyl)-1H-pyrazolo[3,4-b]pyridine-4-carboxamide

HRID 475986Notes

Reaction equation

HRID 475986 reaction equation
Cl[C:2]1[CH:3]=[C:4]([C:14]([NH:16][CH2:17][C:18]2[C:19](=[O:26])[NH:20][C:21]([CH3:25])=[CH:22][C:23]=2[CH3:24])=[O:15])[C:5]2[CH:10]=[N:9][N:8]([CH:11]([CH3:13])[CH3:12])[C:6]=2[N:7]=1.[CH3:27][N:28]([CH3:41])[S:29]([C:32]1[CH:37]=[CH:36][C:35](B(O)O)=[CH:34][CH:33]=1)(=[O:31])=[O:30].C(=O)(O)[O-].[Na+].O>COCCOC.O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl>[CH3:27][N:28]([CH3:41])[S:29]([C:32]1[CH:33]=[CH:34][C:35]([C:2]2[CH:3]=[C:4]([C:14]([NH:16][CH2:17][C:18]3[C:19](=[O:26])[NH:20][C:21]([CH3:25])=[CH:22][C:23]=3[CH3:24])=[O:15])[C:5]3[CH:10]=[N:9][N:8]([CH:11]([CH3:13])[CH3:12])[C:6]=3[N:7]=2)=[CH:36][CH:37]=1)(=[O:30])=[O:31]

Participants

7

Reactant 4

HCID 962WaterHCID 516892Sodium BicarbonateHCID 441193284-(N,N-Dimethylsulphonamido)benzeneboronic acidHCID 565974256-Chloro-N-[(4,6-dimethyl-2-oxo-1,2-dihydro-3-pyridinyl)methyl]-1-(1-methylethyl)-1H-pyrazolo[3,4-b]pyridine-4-carboxamide

Product 1

HCID 565972916-{4-[(Dimethylamino)sulfonyl]phenyl}-N-[(4,6-dimethyl-2-oxo-1,2-dihydro-3-pyridinyl)methyl]-1-(1-methylethyl)-1H-pyrazolo[3,4-b]pyridine-4-carboxamideYield 57.4%

Reagents, catalysts & solvents 2

HCID 178418807HCID 178418807, compoundCatalystHCID 18180031Water 1,2-dimethoxyethaneSolvent

Conditions

Temperature
110 °C

Procedure

In a 25 mL sealable tube under nitrogen were combined 6-chloro-N-[(4,6-dimethyl-2-oxo-1,2-dihydro-3-pyridinyl)methyl]-1-(1-methylethyl)-1H-pyrazolo[3,4-b]pyridine-4-carboxamide (85 mg, 0.23 mmol) and {4-[(dimethylamino)sulfonyl]phenyl}boronic acid (104 mg, 0.46 mmol) in DME/water (3 ml:1 ml). PdCl2(dppf)-CH2Cl2 adduct (9.3 mg, 0.011 mmol) was added and the resulting mixture was degassed with nitrogen for 10 min. Sodium bicarbonate (57.3 mg, 0.68 mmol) was added and the insoluble light brown mixture was heated in an oil bath at 110° C. for 3 hrs. After cooling, 2 mL of water was added to the black mixture and solids that precipitated were filtered. DMF was added along with a few drops of water and solids were filtered. DCM/MeOH (1:1) was added to the grey solids and they were filtered and dried to afford the title compound (69 mg, 57%) as a grayish solid. LCMS E-S (M+H)=523.2. 1H NMR (400 MHz, DMSO-d6) δ ppm 11.59 (br. s., 1H), 9.01 (br. s., 1H), 8.51 (m, J=8.34 Hz, 2H), 8.44 (s, 1H), 8.27 (s, 1H), 7.93 (m, J=8.34 Hz, 2H), 5.91 (s, 1H), 5.36 (dt, J=13.14, 6.57 Hz, 1H), 4.43 (d, J=4.55 Hz, 2H), 2.66 (s, 6H), 2.23 (s, 3H), 2.13 (s, 3H), 1.56 (d, J=6.57 Hz, 6H).

Workup

  1. customIn a 25 mL sealable tube under nitrogen were combined
  2. customthe resulting mixture was degassed with nitrogen for 10 min
  3. temperatureAfter cooling
  4. customthat precipitated
  5. filtrationwere filtered
  6. additionDMF was added along with a few drops of water and solids
  7. filtrationwere filtered
  8. additionDCM/MeOH (1:1) was added to the grey solids and they
  9. filtrationwere filtered
  10. customdried

Sources & evidence

ORD record
ord-12f17be57e984da89fdebb7c089d6c1b
Source dataset
uspto-grants-2014_01
Patent number
US08637509B2

Reaction notes

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