5-morpholin-4-yl-pyrazolo[4,3-b]pyridine derivatives
A pyridyl, phenyl technology, applied in the field of treating diseases, preparing these compounds, and preparing medicines, can solve problems such as lack of ATR inhibitors
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Embodiment 1
[0371] Example 1: 1-methyl-5-((R)-3-methyl-morpholin-4-yl)-7-(6-methyl-pyridin-3-yl)-3-(1H-pyridine Azol-3-yl)-1H-pyrazolo[4,3-b]pyridine (1)
[0372]
[0373] The structural unit used in the synthesis of Example 1: (3R)-3-methyl-4-[1-methyl-7-(6-methylpyridin-3-yl)-1H-pyrazolo[4, 3-b]pyridin-5-yl]morpholine
[0374]
[0375] 1-Methyl-5-[(3R)-3-methylmorpholin-4-yl]-1H-pyrazolo[4,3-b]pyridin-7-yl trifluoromethanesulfonate (1g , 2.37mmol, 1.0 equiv), (6-methylpyridin-3-yl)boronic acid (680mg, 4.72mmol, 1.99 equiv), Pd(dppf)Cl 2 .CH 2 Cl 2 (210 mg, 0.23 mmol, 0.10 equiv) and sodium carbonate (790 mg, 7.08 mmol, 2.99 equiv) were suspended in DMF (12 mL), water (3 mL). The final reaction mixture was heated to 100 °C in the microwave for 1 h. (3R)-3-Methyl-4-[1-methyl-7-(6-methylpyridin-3-yl)-1H-pyrazolo[4,3-b]pyridine- 5-yl]morpholine (600 mg, 70%).
[0376] Structural unit used in the synthesis of Example 1: (3R)-4-[3-bromo-1-methyl-7-(6-methylpyridin-3-yl)-1H-pyraz...
Embodiment 2
[0387] Example 2: 5-((R)-3-methyl-morpholin-4-yl)-7-(6-methyl-pyridin-3-yl)-3-(1H-pyrazol-3-yl )-1H-pyrazolo[4,3-b]pyridine (2)
[0388]
[0389] Structural unit used in the synthesis of Example 2: 6-chloro-2-methyl-3-nitropyridin-4-amine
[0390]
[0391] 2,6-dichloro-3-nitropyridin-4-amine (1g, 4.33mmol, 1 equivalent), Pd(PPh 3 ) 4 (557mg, 0.46mmol, 0.11 equiv) and AlMe 3(2.64 mL, 23.94 mmol, 5.53 equiv) was dissolved in DMF (15 mL) and stirred at 70°C for 3 hours. The reaction was quenched by adding 50 mL of ice / salt. The solids were filtered off. The resulting solution was extracted with ethyl acetate, and the organic layers were combined and concentrated in vacuo. The residue was purified by column chromatography (Method B). 6-Chloro-2-methyl-3-nitropyridin-4-amine was isolated as a yellow solid (500 mg, 55%).
[0392] Building block used in the synthesis of Example 2: 4-bromo-6-chloro-2-methyl-3-nitropyridine
[0393]
[0394] 6-Chloro-2-methyl-3-nitrop...
Embodiment 3
[0418] Example 3: (3R)-3-Methyl-4-[3-(3-methyl-1H-pyrazol-5-yl)-7-(6-methylpyridin-3-yl)-1H- Pyrazolo[4,3-b]pyridin-5-yl]morpholine (3)
[0419] absolute
[0420]
[0421] Structural unit used in the synthesis of Example 3: 5-((R)-3-Methyl-morpholin-4-yl)-7-(6-methyl-pyridin-3-yl)-3-[5 -Methyl-2-(tetrahydro-pyran-2-yl)-2H-pyrazol-3-yl]-1H-pyrazolo[4,3-b]pyridine
[0422]
[0423](3R)-4-[3-iodo-7-(6-methylpyridin-3-yl)-1H-pyrazolo[4,3-b]pyridin-5-yl]-3-methyl phenoline (56 mg; 0.114 mmol; 0.789 equiv) and (3R)-4-[3-iodo-7-(6-methylpyridin-3-yl)-1H-pyrazolo[4,3-b]pyridine- 5-yl]-3-methylmorpholine (15 mg; 0.031 mmol; 0.211 equiv) was dissolved in tetrahydrofuran (1.42 ml) and water (142,00 μl). 1-BOC-3-methylpyrazole-5-boronic acid (49 mg; 0.217 mmol; 1.5 equiv), sodium carbonate (0.02 ml; 0.434 mmol; 3 equiv) and tetrakis(triphenylphosphine)-palladium(0) were added (20 mg; 0.017 mmol; 0.120 equiv). The reaction suspension was stirred at 80°C for 1 hour. Add 3-methy...
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