1,4-Dioxane → HCID 68079252, compound

HRID 476114Notes

Reaction equation

HRID 476114 reaction equation
[CH3:1][C:2]([N:5]1[C:9]2[N:10]=[C:11](OS(C(F)(F)F)(=O)=O)[CH:12]=[C:13]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[C:8]=2[C:7]([CH3:27])=[N:6]1)([CH3:4])[CH3:3].[N:28]1[CH:33]=[CH:32][CH:31]=[C:30](B(O)O)[CH:29]=1.C([O-])(O)=O.[Na+].O1CCOCC1>CCOC(C)=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>[CH3:1][C:2]([N:5]1[C:9]2[N:10]=[C:11]([C:30]3[CH:29]=[N:28][CH:33]=[CH:32][CH:31]=3)[CH:12]=[C:13]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[C:8]=2[C:7]([CH3:27])=[N:6]1)([CH3:4])[CH3:3]

Participants

7

Reactant 4

HCID 312751,4-DioxaneHCID 516892Sodium BicarbonateHCID 27343783-Pyridinylboronic acidHCID 86677625HCID 86677625, compound

Product 1

HCID 68079252HCID 68079252, compound

Reagents, catalysts & solvents 2

HCID 178418807HCID 178418807, compoundCatalystHCID 8857Ethyl AcetateSolvent

Procedure

Ethyl 1-(1,1-dimethylethyl)-3-methyl-6-{[(trifluoromethyl)sulfonyl]oxy}-1H-pyrazolo[3,4-b]pyridine-4-carboxylate (100 mg, 0.244 mmol), 3-pyridinylboronic acid (39.0 mg, 0.318 mmol), aq. saturated NaHCO3 (1 mL) and 1,4-dioxane (3 mL) were degassed with nitrogen (10 min) followed by addition of PdCl2(dppf)-CH2Cl2 adduct (9.97 mg, 0.012 mmol). The sealed mixture was irradiated (microwave) at 120° C. for 40 min. The reaction mixture was diluted with EtOAc and filtered. The filtrate was concentrated in vacuo and the crude residue was purified by silica gel chromatography (0 to 100% EtOAc/hexanes). The final product was collected as a solid, 72 mg (87%). LCMS E-S (M+H)=339.3. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.46-1.57 (m, 3H), 1.90 (s, 9H), 2.72 (s, 3H), 4.45-4.64 (m, 2H), 7.47 (dd, J=8.08, 4.80 Hz, 1H), 8.03 (s, 1H), 8.46 (dt, J=8.08, 2.02 Hz, 1H), 8.72 (dd, J=4.80, 1.52 Hz, 1H), 9.43 (d, J=1.52 Hz, 1H).

Workup

  1. customThe sealed mixture was irradiated (microwave) at 120° C. for 40 min
  2. filtrationfiltered
  3. concentrationThe filtrate was concentrated in vacuo
  4. customthe crude residue was purified by silica gel chromatography (0 to 100% EtOAc/hexanes)
  5. customThe final product was collected as a solid, 72 mg (87%)

Sources & evidence

ORD record
ord-3e1f2e6b1bfb4c0e96ad2c2e534a946e
Source dataset
uspto-grants-2014_01
Patent number
US08637509B2

Reaction notes

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