1,10-Phenanthroline → tert-butyl 4-(3-((2,2-dimethyl-1,3-dioxolan-4-yl)methoxy)-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate

HRID 387575Notes

Reaction equation

HRID 387575 reaction equation
I[C:2]1[C:10]2[C:5](=[N:6][CH:7]=[CH:8][C:9]=2[N:11]2[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH2:12]2)[N:4]([CH2:24][C:25]2[CH:30]=[CH:29][C:28]([O:31][CH3:32])=[CH:27][CH:26]=2)[N:3]=1.N1C2C(=CC=C3C=2N=CC=C3)C=CC=1.[CH3:47][C:48]1([CH3:55])[O:52][CH:51]([CH2:53][OH:54])[CH2:50][O:49]1.[F-].[K+]>C1(C)C=CC=CC=1.C(OCC)(=O)C>[CH3:47][C:48]1([CH3:55])[O:52][CH:51]([CH2:53][O:54][C:2]2[C:10]3[C:5](=[N:6][CH:7]=[CH:8][C:9]=3[N:11]3[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH2:12]3)[N:4]([CH2:24][C:25]3[CH:30]=[CH:29][C:28]([O:31][CH3:32])=[CH:27][CH:26]=3)[N:3]=2)[CH2:50][O:49]1

Participants

7

Reactant 4

HCID 13181,10-PhenanthrolineHCID 7528SolketalHCID 522689Potassium FluorideHCID 68759242tert-butyl 4-(3-iodo-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate

Product 1

HCID 68763362tert-butyl 4-(3-((2,2-dimethyl-1,3-dioxolan-4-yl)methoxy)-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylateYield 56.3%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of tert-Butyl 4-(3-iodo-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate (0.12 g, 0.218 mmol, see Example 5), Cu(I)I (0.0416 g, 0.218 mmol), 1,10-phenanthroline (0.0393 g, 0.218 mmol), (2,2-dimethyl-1,3-dioxolan-4-yl)methanol (0.812 mL, 6.55 mmol) and KF on Al2O3 (40%; 0.222 g, 1.53 mmol) in toluene (4 mL) was stirred at 120° C. for 75 hours. Ethyl acetate (10 mL) was then added, and the reaction was filtered through a pad of celite. The filtrate was then concentrated to dryness. The resulting residue was purified by chromatography (hexane:ethyl acetate, 1:1) to give tert-butyl 4-(3-((2,2-dimethyl-1,3-dioxolan-4-yl)methoxy)-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyridin-4-yl)piperazine-1-carboxylate (0.068 g, 56%) as a solid. MS APCI (+) m/z 554.4 detected.

Workup

  1. filtrationthe reaction was filtered through a pad of celite
  2. concentrationThe filtrate was then concentrated to dryness
  3. customThe resulting residue was purified by chromatography (hexane:ethyl acetate, 1:1)

Sources & evidence

ORD record
ord-d31a64caa55f487f95f8534b6ab97515
Source dataset
uspto-grants-2013_02
Patent number
US08372842B2

Reaction notes

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