HCV Inhibitors
A technology of excipients and compounds, applied in the field of hepatitis C virus inhibitors, can solve the problems of reduced antiviral efficacy of HCV protease inhibitors and the like
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Embodiment 1
[0670] Example 1. (1aS, 2aR, 6S, 9S, 11R, 23aR, 23bS)-6-tert-butyl-N-[(1R,2R)-1-[(cyclopropylsulfonyl)carbamoyl]- 2-(Difluoromethyl)cyclopropyl]-15-methoxy-4,7-dioxo-1a,2,2a,4,5,6,7,10,11,19,20,21 ,22,23,23a,23b-Hexadecahydro-1H,9H-8,11-methylenecyclopropano[4',5']cyclopenta[1',2':18,19][ Preparation of 1,10,3,6]dioxadiazacyclonadecano(nonadecino)[11,12-b]quinoxaline-9-carboxamide.
[0671]
[0672]
[0673] Example 1
[0674] Step 1. Preparation of 1-1. Combine quinoxaline C1 (2.29g, 10.0mmol) with N-Boc-trans-4-hydroxy-L-proline methyl ester (2.65g, 11.0mmol) and Cs 2 CO 3 (3.59 g, 11.0 mmol) were combined as a suspension in MeCN (20 mL). The stirred reaction mixture was heated to 85 °C for 16 h, then filtered through celite and concentrated in vacuo. The crude residue was purified by silica gel chromatography (5%-50% EtOAc / Hex) to give 1-1.LCMS-ESI + (m / z): [M-Boc+2H] + Calculated value C 15 h 17 ClN 3 o 4 : 338.09; measured value: 337.94.
[0675] Step 2....
Embodiment 2
[0682] Example 2. (1aS, 2aR, 6S, 9S, 11R, 23aR, 23bS)-6-tert-butyl-N-[(1R,2R)-2-(difluoromethyl)-1-{[(1 -methylcyclopropyl)sulfonyl]carbamoyl}cyclopropyl]-15-methoxy-4,7-dioxo-1a,2,2a,4,5,6,7,10,11 ,19,20,21,22,23,23a,23b-Hexadecahydro-1H,9H-8,11-methylenecyclopropane[4',5']cyclopenta[1',2' : Preparation of 18,19][1,10,3,6]dioxadiazacyclonadecano[11,12-b]quinoxaline-9-carboxamide.
[0683]
[0684] Example 2
[0685] Example 2 was prepared in a similar manner to Example 1, replacing Intermediate A9 in Step 8 with Intermediate A10. Example 2 (107 mg) was isolated as the TFA salt. Analytical HPLC retention time: 8.85min. LCMS-ESI + (m / z): [M+H] + Calculated value C 41 h 55 f 2 N 6 o 9 S: 845.37; measured value: 845.67. 1 H-NMR (400MHz, CD 3 OD)δ9.31(s,1H),7.78(d,J=8.8Hz,1H),7.20(dt,J=3.9,2.6Hz,2H),6.06(t,J=3.5Hz,1H),5.87 (td,J=55.8,6.7Hz,1H),5.00(d,J=7.5Hz,1H),4.51–4.38(m,2H),4.34(s,1H),4.11(dd,J=11.8,3.8 Hz,1H),3.92(s,3H),3.04–2.85(m,1H),2.85–2.67(m,1H),2.49(d...
Embodiment 3
[0686] Example 3. (1aS, 2aR, 6S, 9S, 11R, 23aR, 23bS)-6-tert-butyl-N-[(1R,2S)-1-[(cyclopropylsulfonyl)carbamoyl]- 2-(2,2-Difluoroethylcyclopropyl)-15-methoxy-4,7-dioxo-1a,2,2a,4,5,6,7,10,11,19, 20,21,22,23,23a,23b-Hexadeca-hydro-1H,9H-8,11-methylenecyclopropano[4',5']cyclopenta[1',2':18 ,19][1,10,3,6]dioxadiazacyclonadecano[11,12-b]quinoxaline-9-carboxamide.
[0687]
[0688] Example 3
[0689] Example 3 was prepared in a similar manner to Example 1, substituting Intermediate A7 for Intermediate A9 in Step 8. Example 3 (52 mg) was isolated as the TFA salt. Analytical HPLC retention time: 8.82min. LCMS-ESI + (m / z): [M+H] + Calculated value C 41 h 55 f 2 N 6 o 9 S: 845.37; measured value: 845.96. 1 H-NMR (400MHz, CD 3 OD)δ9.18(s,1H),7.78(dd,J=8.1,1.5Hz,1H),7.26–7.16(m,2H),6.07(t,J=3.6Hz,1H),5.89(tt, J=56.5, 4.1Hz, 1H), 4.99(d, J=7.5Hz, 1H), 4.45(dd, J=11.1, 5.9Hz, 2H), 4.32(s, 1H), 4.11(dd, J=11.9 ,3.8Hz,1H),3.92(s,3H),3.04–2.86(m,2H),2.86–2.68(m,1H),2.47(dd,J=...
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