Participants
| Role | Name | HCID | Charge |
|---|
| Reactant | Aniline | HCID 6115 | — |
| Reactant | Trifluoroacetic acid | HCID 6422 | — |
| Reactant | Lithium Hexamethyldisilazide | HCID 2733832 | — |
| Reactant | HCID 89783190 | HCID 89783190 | — |
| Product | HCID 89784140 | HCID 89784140 | 23.9% |
Reaction Steps
A mixture of 2-(2-chloroquinolin-8-yl)-7-ethyl-6,7-dihydro-1H-pyrrolo[3,2-c]pyridin-4(5H)-one (Example 22; 0.075 g, 0.230 mmol) and aniline (0.105 ml, 1.151 mmol) was treated with LHMDS (1.0 M in THF; 1.151 ml, 1.151 mmol) at RT. After 2 h, the reaction was concentrated, then dissolved in DMSO and treated with TFA (0.089 ml, 1.151 mmol). This material was purified by rpHPLC (Phenomenex Gemini 150×30 mm C18 column, 10-70% ACN/H2O with 0.1% TFA); product-containing fractions were treated with saturated aq. NaHCO3 and DCM. The organic layer was separated, and the aq. layer was extracted 3×DCM. The combined organic layers were then dried over Na2SO4, filtered, and concentrated in vacuo to give rac-7-ethyl-2-(2-(phenylamino)quinolin-8-yl)-6,7-dihydro-1H-pyrrolo[3,2-c]pyridin-4(5H)-one (0.021 g, 0.055 mmol, 23.85% yield): 1H NMR (400 MHz, DMSO-d6) δ ppm 12.24 (1H, br. s), 9.53 (1H, s), 8.12 (1H, d, J=9.0 Hz), 7.96 (1H, dt, J=7.5, 0.6 Hz), 7.53-7.67 (3H, m), 7.39 (2H, t, J=7.8 Hz), 7.29 (1H, t, J=7.6 Hz), 7.03-7.15 (2H, m), 6.86-6.95 (2H, m), 3.46-3.61 (1H, m), 3.06-3.21 (1H, m), 2.58-2.71 (1H, m), 1.15-1.32 (2H, m), 0.66 (3H, t, J=7.3 Hz). m/z (ESI, +ve) 383.0 (M+H)+. A portion of this material was resolved by chiral SFC (Chiralpak IC (21×250 mm, 5 μm); additive in supercritical fluid CO2 was 50% MeOH with 20 mM NH3; 60 mL/min; column temperature 40° C.; outlet pressure 100 bar) to give separated enantiomers (R)-7-ethyl-2-(2-(phenylamino)quinolin-8-yl)-6,7-dihydro-1H-pyrrolo[3,2-c]pyridin-4(5H)-one (Example 25) and (S)-7-ethyl-2-(2-(phenylamino)quinolin-8-yl)-6,7-dihydro-1H-pyrrolo[3,2-c]pyridin-4(5H)-one. (Example 26).
Provenance & Evidence
| DOI | 10.6084/m9.figshare.5104873.v1 |
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| Patent number | US09394297B2 |
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| Source dataset | uspto-grants-2016_07 |
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| ORD ID | ord-ee90b80a7685433484285c41d24ad5fc |
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| Source note | uspto-grants-2016_07 |
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