Triethylamine → 1-(4-fluorophenyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazolo[3,4-b]pyridine

HRID 1186832Notes

Reaction equation

HRID 1186832 reaction equation
C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1.[F:30][C:31]1[CH:36]=[CH:35][C:34]([N:37]2[C:41]3=[N:42][CH:43]=[CH:44][C:45](I)=[C:40]3[CH:39]=[N:38]2)=[CH:33][CH:32]=1.C(N(CC)CC)C.[CH3:54][C:55]1([CH3:62])[C:59]([CH3:61])([CH3:60])[O:58][BH:57][O:56]1>CC#N.CC#N.Cl[Pd]Cl>[F:30][C:31]1[CH:36]=[CH:35][C:34]([N:37]2[C:41]3=[N:42][CH:43]=[CH:44][C:45]([B:57]4[O:58][C:59]([CH3:61])([CH3:60])[C:55]([CH3:62])([CH3:54])[O:56]4)=[C:40]3[CH:39]=[N:38]2)=[CH:33][CH:32]=1

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 27347684,4,5,5-Tetramethyl[1,3,2]dioxaborolaneHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 666684371-(4-Fluorophenyl)-4-iodo-1H-pyrazolo[3,4-B]pyridine

Product 1

HCID 666680341-(4-fluorophenyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazolo[3,4-b]pyridine

Reagents, catalysts & solvents 1

HCID 6093782Bis(acetonitrile)dichloropalladiumCatalyst

Conditions

Temperature
110 °C

Procedure

A vial was charged with bis(acetonitrile)palladium(II) chloride (1.038 mg, 4.00 μmol), dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine (3.28 mg, 8.00 μmol), and Intermediate 2A (0.068 g, 0.200 mmol). The vial was capped with a rubber septum and then evacuated and backfilled with N2 (this sequence was carried out a total of 2 times). Dioxane (0.120 mL) was added via syringe, through the septum, followed by the addition of triethylamine (0.084 mL, 0.600 mmol) and 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.044 mL, 0.300 mmol) dropwise. The septum was then replaced with a Teflon screw valve, and the vial sealed. The reaction mixture was heated at 110° C. After 14 h, the reaction mixture was allowed to cool to room temperature. The reaction mixture was filtered through a disposable fritted funnel and the filter cake washed with CH2Cl2. The filtrate was concentrated to afford the title compound as a yellow solid. Intermediate 105B: MS (ESI): m/z=340.2 [M+H]+ HPLC Peak ret. T=2.00 minutes was product. (HPLC conditions: Column:Luna C18 4.6×30 mm 3 u A:10:90 H2O:ACN NH4OAc/B:10:90 H2O:ACN NH4OAc; 0%-95% B in 2 min; 4 mL/min flow).

Workup

  1. customThe vial was capped with a rubber septum
  2. customevacuated
  3. additionDioxane (0.120 mL) was added via syringe, through the septum
  4. temperatureto cool to room temperature
  5. filtrationThe reaction mixture was filtered through a disposable fritted funnel
  6. washthe filter cake washed with CH2Cl2
  7. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-12fdd4cbe6f54b4fa87b6fcb444ada2f
Source dataset
uspto-grants-2014_03
Patent number
US08673922B2

Reaction notes

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