Fused imidazo-piperidine jak inhibitors
A compound, -OH technology, applied in the field of treating respiratory diseases and preparing such compounds, can solve problems such as poor results and unapproved treatments
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[0216] The following synthetic and biological examples are provided to illustrate the invention and are not to be construed as limiting the scope of the invention in any way. In the examples below, the following abbreviations have the following meanings unless otherwise indicated. Abbreviations not defined below have their generally accepted meanings.
[0217] ACN = acetonitrile
[0218] DCM = dichloromethane
[0219] DIPEA=N,N-Diisopropylethylamine
[0220] DMF=N,N-Dimethylformamide
[0221] EtOAc = ethyl acetate
[0222] h = hour
[0223] HATU = N,N,N',N'-tetramethyl-O-(7-azabenzotriazol-1-yl) hexafluorophosphate
[0224] IPA = isopropyl alcohol
[0225] IPAc = isopropyl acetate
[0226] MeOH = Methanol
[0227] min=minute
[0228] Pd(PPh 3 ) 4 =Tetrakis(triphenylphosphine)palladium(0)
[0229] RT = room temperature
[0230] TFA = trifluoroacetic acid
[0231] THF = Tetrahydrofuran
[0232] Bis(pinacol radical) diboron = 4,4,5,5,4',4',5',5'-octamethyl-[2,2'...
example 1
[0299] Example 1: ((S)-2-(6-(2-Ethyl-5-fluoro-4-hydroxyphenyl)-1H-indazol-3-yl)-5-propyl-4,5,6 ,7-tetrahydro-3H-imidazo[4,5-c]pyridin-6-yl)((1S,4S)-5-methyl-2,5-diazabicyclo-[2.2.1]heptane Alk-2-yl)methanone
[0300]
[0301] To (S)-2-(6-(2-ethyl-5-fluoro-4-hydroxyphenyl)-1H-indazol-3-yl)-5-propyl-4,5,6,7- Tetrahydro-3H-imidazo[4,5-c]pyridine-6-carboxylic acid, TFA (30mg, 0.052mmol), (1S,4S)-5-methyl-2,5-diazabicyclo[2.2. 1] To a solution of heptane dihydrobromide (42.7mg, 0.156mmol) and DIPEA (0.064ml, 0.364mmol) in DMF (1.5ml) was added HATU (29.6mg, 0.078mmol) and the reaction was stirred at room temperature The mixture was left overnight. Hydrazine (5 equiv) was added, the reaction mixture was concentrated and purified by preparative HPLC to afford the TFA salt of the title compound (27 mg, 66% yield). C 31 h 36 FN 7 o 2 (m / z):[M+H] + Calculated value 558.29 experimental value 558.3. 1 H NMR (400MHz, methanol-d 4 )δ8.17(dt,1H),7.59-7.50(m,1H),7.32(dd,1H),6.95...
example 3
[0302] Example 3: ((S)-3-(dimethylamino)pyrrolidin-1-yl)((S)-5-ethyl-2-(6-(2-ethyl-5-fluoro-4- Hydroxyphenyl)-1H-indazol-3-yl)-4,5,6,7-tetrahydro-3H-imidazo[4,5-c]pyridin-6-yl)methanone
[0303]
[0304] To (S)-2-(6-(2-ethyl-5-fluoro-4-hydroxyphenyl)-1H-indazol-3-yl)-5 isopropyl-4,5,6,7- Tetrahydro-3H-imidazo[4,5-c]pyridine-6-carboxylic acid, TFA (179mg, 0.310mmol), (S)-N,N-dimethylpyrrolidin-3-amine (0.079mL, 0.620 mmol) and DIPEA (0.162 mL 0.930 mmol) in DMF (4 mL) was added HATU (177 mg, 0.465 mmol) and the reaction mixture was stirred at room temperature overnight. Hydrazine (5 equiv) was added, the reaction mixture was concentrated and purified by preparative HPLC to afford the TFA salt of the title compound (107 mg, 44% yield). C 31 h 38 FN 7 o 2 (m / z):[M+H] + The calculated value is 560.31 and the experimental value is 560.2. 1 H NMR (400MHz, methanol-d 4 )δ8.21(d,1H),7.50(s,1H),7.26(d,1H),6.94(d,1H),6.90(d,1H),4.83-4.66(m,1H),4.48-4.25 (m,2H),4.23-4.12(m,1...
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