Potassium Acetate → 3-bromo-1-trityl-1H-pyrazolo[3,4-b]pyridine

HRID 539924Notes

Reaction equation

HRID 539924 reaction equation
[Br:1][C:2]1[C:10]2[C:5](=[N:6][CH:7]=[C:8](F)[CH:9]=2)[N:4]([C:12]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[N:3]=1.CC([O-])=O.[K+].CC1(C)C(C)(C)OB(B2OC(C)(C)C(C)(C)O2)O1>CN(C=O)C.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]>[Br:1][C:2]1[C:10]2[C:5](=[N:6][CH:7]=[CH:8][CH:9]=2)[N:4]([C:12]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)[C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[N:3]=1

Participants

6

Reactant 3

HCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 712512553-bromo-5-fluoro-1-trityl-1H-pyrazolo[3,4-b]pyridine

Product 1

HCID 679755003-bromo-1-trityl-1H-pyrazolo[3,4-b]pyridine

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

A solution of 3-bromo-5-fluoro-1-trityl-pyrazolo[3,4-b]pyridine, 44, (16.86 g, 36.79 mmol), KOAc (10.83 g, 110.4 mmol) and 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane (14.01 g, 55.18 mmol) in DMF (250 mL) was degassed under a nitrogen stream for 40 min. To the mixture was added Pd(dppf)2Cl2 (3.00 g, 3.68 mmol). The reaction mixture was heated at 100° C. for 90 minutes. The reaction mixture was filtered through a pad of florisil and celite. The filtrate was diluted with ether and brine. The organic phase was dried over MgSO4, filtered and concentrated in vacuo. The product was dried on high vacuum pump 3 days. To the product was added 200 mL Et2O and the mixture was stirred and filtered. The filtrate was concentrated in vacuo. The crude residue was diluted with 150 mL hexanes and the suspension was stirred for 3 hours, filtered and concentrated in vacuo to afford 12.6 g of desired product.

Workup

  1. filtrationThe reaction mixture was filtered through a pad of florisil and celite
  2. additionThe filtrate was diluted with ether and brine
  3. dry with materialThe organic phase was dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe product was dried on high vacuum pump 3 days
  7. additionTo the product was added 200 mL Et2O
  8. filtrationfiltered
  9. concentrationThe filtrate was concentrated in vacuo
  10. additionThe crude residue was diluted with 150 mL hexanes
  11. stirringthe suspension was stirred for 3 hours
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-29fe0cd76f9e41ec9231f882338ceefa
Source dataset
uspto-grants-2014_10
Patent number
US08871774B2

Reaction notes

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