Tetrabutylammonium Fluoride → 4-Methyl-3-(1-methyl-1H-pyrazolo[3,4-c]pyridin-4-ylethynyl)-phenylamine

HRID 446922Notes

Reaction equation

HRID 446922 reaction equation
Br[C:2]1[CH:7]=[N:6][CH:5]=[C:4]2[N:8]([CH3:11])[N:9]=[CH:10][C:3]=12.C[Si]([C:16]#[C:17][C:18]1[CH:19]=[C:20]([NH2:24])[CH:21]=[CH:22][CH:23]=1)(C)C.[F-].[CH2:26]([N+](CCCC)(CCCC)CCCC)CCC>C1COCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[CH3:26][C:23]1[CH:22]=[CH:21][C:20]([NH2:24])=[CH:19][C:18]=1[C:17]#[C:16][C:2]1[CH:7]=[N:6][CH:5]=[C:4]2[N:8]([CH3:11])[N:9]=[CH:10][C:3]=12

Participants

7

Reactant 3

HCID 2724141Tetrabutylammonium FluorideHCID 111597943-[2-(Trimethylsilyl)ethynyl]anilineHCID 576069364-Bromo-1-methyl-1H-pyrazolo(3,4-c)pyridine2×

Product 1

HCID 595364374-Methyl-3-(1-methyl-1H-pyrazolo[3,4-c]pyridin-4-ylethynyl)-phenylamineYield 58.5%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
80 °C

Procedure

In an adaption of GP 3c, 640 mg of 4-bromo-1-methyl-1H-pyrazolo[3,4-c]pyridine (Intermediate 2.1, 3 mmol, 1 eq), 1000 mg 3-trimethylsilanylethynyl-phenylamine (4.92 mmol, 1.63 eq.), 106 mg dichlorobis(triphenylphosphine)palladium (II) (PdCl2(PPh3)2) (0.15 mmol, 5 mol %) and 115 mg copper (I) iodide (0.6 mmol, 0.2 eq.) were dissolved in 15 mL THF (0.2 M) and treated with 3.6 mL tetra-n-butylammonium fluoride solution (1.0 M in THF, 3.6 mmol, 1.2 eq.). The resulting mixture was heated to 80° C. in a Biotage Initiator microwave oven for 30 min. Extractive work-up followed by column chromatography provided the 460 mg of the target compound (58% yield).

Sources & evidence

ORD record
ord-0f56cb9feb0a4d4cacf64708b2641f9a
Source dataset
uspto-grants-2013_07
Patent number
US08481539B2

Reaction notes

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