Diisopropylethylamine → 2-(4-(2,4-difluorophenoxy)piperidin-1-yl)-3-(isopropylamino)-6-(methyl-L-prolyl)-5,6,7,8-tetrahydropyrido[3,4-b]pyrazine
Reaction equation
[CH3:1][N:2]1[CH2:6][CH2:5][CH2:4][C@H:3]1[C:7]([OH:9])=O.CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.CCN(C(C)C)C(C)C.OC(C(F)(F)F)=O.[F:50][C:51]1[CH:77]=[C:76]([F:78])[CH:75]=[CH:74][C:52]=1[O:53][CH:54]1[CH2:59][CH2:58][N:57]([C:60]2[N:61]=[C:62]3[CH2:73][CH2:72][NH:71][CH2:70][C:63]3=[N:64][C:65]=2[NH:66][CH:67]([CH3:69])[CH3:68])[CH2:56][CH2:55]1>CC(N(C)C)=O>[F:50][C:51]1[CH:77]=[C:76]([F:78])[CH:75]=[CH:74][C:52]=1[O:53][CH:54]1[CH2:55][CH2:56][N:57]([C:60]2[N:61]=[C:62]3[CH2:73][CH2:72][N:71]([C:7](=[O:9])[C@@H:3]4[CH2:4][CH2:5][CH2:6][N:2]4[CH3:1])[CH2:70][C:63]3=[N:64][C:65]=2[NH:66][CH:67]([CH3:69])[CH3:68])[CH2:58][CH2:59]1Participants
Reactant 4
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 60 °C
Procedure
A solution of (S)-1-methylpyrrolidine-2-carboxylic acid (16.8 mg, 0.130 mmol) in DMA (0.4 mL) was treated with HATU (49.6 mg, 0.130 mmol) and DIPEA (45.6 μL, 0.261 mmol) at room temperature. To this was added a solution of 2-(4-(2,4-difluorophenoxyl)piperidin-1-yl)-N-isopropyl-5,6,7,8-tetrahydropyrido[3,4-b]pyrazin-3-amine TFA salt (45 mg, 0.087 mmol) in DMA (0.47 mL). The reaction mixture was stirred at 60° C. for 45 min. The reaction mixture was allowed to cool to room temperature and was purified directly directly by HPLC Method B, with the exception that a Phenomenex Gemini® C18, 5 μm, ID 30×75 mm column was used, using a 25% to 60% ACN gradient to give the title compound, as a TFA salt, as a white solid (2.8 mg, 5.1%). 1H NMR (400 MHz, methanol-d4) δ ppm 1.26 (dd, J=6.6, 4.5 Hz, 6H), 1.97 (m, 4H), 2.09 (m, 3H), 2.24 (m, 1H), 2.76 (m, 3H), 2.93 (app d, J=7.6 Hz, 3H), 3.03 (m, 2H), 3.20 (m, 1H), 3.40 (m, 2H), 3.69-4.19 (m, 4H), 4.48 (m, 2H), 4.66 (m, 2H), 6.87 (m, 1H), 6.98 (ddd, J=11.2, 8.5, 3.0 Hz, 1H), 7.17 (td, J=9.2, 5.6 Hz, 1H); ESI-MS m/z [M+H]+ 515.6.
Workup
- temperatureto cool to room temperature
- customwas purified directly directly by HPLC Method B, with the exception that a Phenomenex Gemini® C18, 5 μm, ID 30×75 mm column
Sources & evidence
- ORD record
- ord-46446be2aa434d62bb0da04d50786500
- Source dataset
- uspto-grants-2015_11
- Patent number
- US09181249B2
Reaction notes
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