2,4-disubstituted pyrimidine derivatives as cdk inhibitors and their applications
A technology of pyrimidine derivatives and di-substitution, applied in 2 fields, can solve problems such as severe toxicity and side effects
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Embodiment 1
[0058] Compound (I-1) N-(5-(4-ethylpiperazine-1-methyl)-pyridin-2-yl)-5-fluoro-4-(1-isopropyl-1H-indole- 5-yl)pyrimidin-2-amine
[0059] Step 1: 5-bromoindole (1.0g, 5.1mmol), 2-bromopropane (0.94g, 7.65mmol), potassium hydroxide (0.43g, 7.65mmol) were added to N,N-dimethylformamide (DMF , 10mL), N 2 Under protection, react at 70°C for 10h. Add H to the reaction solution 2 O (50mL) / ethyl acetate (50mL) was stirred and extracted, the organic layer was dried, filtered, concentrated and passed through a silica gel column (eluent ethyl acetate / petroleum ether: 1 / 30-1 / 10) to obtain a white solid 1-iso Propyl-5-bromo-1H-indole (0.8 g, yield 66%).
[0060] Step 2: 1-isopropyl-5-bromo-1H-indole (0.8g, 3.36mmol), bisboronic acid pinacol ester (1.02g, 4.0mmol), Pd(dppf)Cl 2 (0.25g, 0.34mmol), potassium acetate (0.66g, 6.72mmol) were added in 1,4-dioxane (15mL), N 2 Reaction at 80°C for 5h under protection. Concentrate the solvent to dryness, add H to the residue 2 O (50mL) / ethyl...
Embodiment 2
[0064] Compound (I-2) N-(5-(piperazin-1-yl)-pyridin-2-yl)-5-fluoro-4-(1-isopropyl-1H-indol-5-yl)pyrimidine -2-amine
[0065] The synthesis of compound I-2 is carried out according to the method of Example 1, and the starting materials are 1-isopropyl-5-(2-chloro-5-fluoropyrimidin-4-yl)-1H-indole and 4-(6- Aminopyridin-3-yl)piperazine-1-carboxylate tert-butyl ester, after reacting in step 4 of Example 1, N-(5-(4-carboxylate tert-butyl ester-1-piperazinyl)-pyridine- 2-yl)-5-fluoro-4-(1-isopropyl-1H-indol-5-yl)pyrimidin-2-amine, the intermediate was de-BOC-protected with 3N hydrochloric acid ethyl acetate to give light Yellow solid target product N-(5-(piperazin-1-yl)-pyridin-2-yl)-5-fluoro-4-(1-isopropyl-1H-indol-5-yl)pyrimidine-2 - Amine hydrochloride (I-2). MS(m / z): 432[M+H] + . 1 H NMR (DMSO-d 6 ): δ: 11.65 (br, 1H), 9.70 (br, 2H), 8.77-8.76 (d, J=4.0Hz, 1H), 8.39 (s, 1H), 8.01-8.00 (d, J=4.0Hz, 1H), 7.96(s, 1H), 7.93(s, 1H), 7.85-7.83(d, J=8.0Hz, 1H), 7.76-7.74(d, J=8...
Embodiment 3
[0067] Compound (I-3) N-(5-(piperazin-1-yl)-pyridin-2-yl)-5-fluoro-4-(1-cyclopentyl-3-acetyl-1H-indole- 5-yl)pyrimidin-2-amine
[0068] The synthesis of compound I-3 is carried out according to the method in Example 1, and the starting material is 1-cyclopentyl-3-acetyl-5-(2-chloro-5-fluoropyrimidin-4-yl)-1H-indole ( Synthetic method is similar to embodiment 1, and starting material is 2,4-dichloro-5-fluoropyrimidine and 1-cyclopentyl-3-acetyl-5-boronic acid pinacol ester-1H-indole (starting Starting materials are bromocyclopentane and 3-acetyl-5-bromo-1H-indole)) and tert-butyl 4-(6-aminopyridin-3-yl)piperazine-1-carboxylate. The target product N-(5-(piperazin-1-yl)-pyridin-2-yl)-5-fluoro-4-(1-cyclopentyl-3-acetyl-1H-indole- 5-yl)pyrimidin-2-amine hydrochloride (I-3). MS(m / z): 500[M+H] + . 1 H NMR (DMSO-d 6 ): δ: 11.67 (br, 1H), 9.73 (br, 2H), 9.39 (s, 1H), 8.78 (s, 1H), 8.69-8.67 (d, J=8.0Hz, 1H), 8.00-7.97 ( m, 2H), 7.93(s, 1H), 7.72-7.69(m, 2H), 4.89-4.83(m, 1H), 3....
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