Sodium Carbonate → 1-[1-(3-Bromo-5-chloro-2-methoxy-4-methylphenyl)ethyl]-3-vinyl-1H-pyrazolo[3,4-d]pyrimidin-4-amine

HRID 1499843Notes

Reaction equation

HRID 1499843 reaction equation
[Br:1][C:2]1[C:3]([O:23][CH3:24])=[C:4]([CH:10]([N:12]2[C:16]3=[N:17][CH:18]=[N:19][C:20]([NH2:21])=[C:15]3[C:14](I)=[N:13]2)[CH3:11])[CH:5]=[C:6]([Cl:9])[C:7]=1[CH3:8].C(=O)([O-])[O-].[Na+].[Na+].O1CCO[CH2:33][CH2:32]1>O.Cl[Pd](Cl)(P(C(C)(C)C)(C(C)(C)C)C1C=CC(N(C)C)=CC=1)P(C1C=CC(N(C)C)=CC=1)(C(C)(C)C)C(C)(C)C>[Br:1][C:2]1[C:3]([O:23][CH3:24])=[C:4]([CH:10]([N:12]2[C:16]3=[N:17][CH:18]=[N:19][C:20]([NH2:21])=[C:15]3[C:14]([CH:32]=[CH2:33])=[N:13]2)[CH3:11])[CH:5]=[C:6]([Cl:9])[C:7]=1[CH3:8]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 312751,4-DioxaneHCID 866777661-[1-(3-Bromo-5-chloro-2-methoxy-4-methylphenyl)ethyl]-3-iodo-1H-pyrazolo[3,4-d]pyrimidin-4-amine

Product 1

HCID 866777671-[1-(3-Bromo-5-chloro-2-methoxy-4-methylphenyl)ethyl]-3-vinyl-1H-pyrazolo[3,4-d]pyrimidin-4-amine

Reagents, catalysts & solvents 2

HCID 178482906HCID 178482906, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
95 °C

Procedure

Dichloro(bis{di-tert-butyl[4-(dimethylamino)phenyl]phosphoranyl})palladium (12 mg, 0.017 mmol) was added to a mixture of vinyl boronic acid MIDA (110 mg, 0.6 mmol, from Aldrich, item #704415), 1-[1-(3-bromo-5-chloro-2-methoxy-4-methylphenyl)ethyl]-3-iodo-1H-pyrazolo[3,4-d]pyrimidin-4-amine (0.30 g, 0.57 mmol) and sodium carbonate (0.14 g, 1.1 mmol) in 1,4-dioxane (1 mL) and water (0.1 mL) and then the reaction was degassed with N2 3 times. The reaction was stirred at 95° C. for 4 h. The mixture was diluted with methylene chloride, washed with sat. NaHCO3, water, brine, dried over Na2SO4, filtered and concentrated. The product was purified by chromatography eluting with CH2Cl2/EtOAc (max. EtOAc 60%). LCMS calculated for C17H18BrClN5O (M+H)+: m/z=422.0; Found: 422.2.

Workup

  1. customthe reaction was degassed with N2 3 times
  2. additionThe mixture was diluted with methylene chloride
  3. washwashed with sat. NaHCO3, water, brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe product was purified by chromatography
  8. washeluting with CH2Cl2/EtOAc (max. EtOAc 60%)

Sources & evidence

ORD record
ord-fd23fdcc5d1741a7b19d80d7bcb334e1
Source dataset
uspto-grants-2015_12
Patent number
US09199982B2

Reaction notes

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