T.V. Salnikova, A.A. Sabitov, M.V. Dmitriev et al.
Tetrahedron 88 (2021) 132129
4.9.4. Methyl 2-(2-amino-1-cyano-2-oxoethyl)-2-(4-
chlorophenyl)-4-(4-hydroxy-1-methyl-2-oxo-1,2-dihydroquinolin-
3-yl)-5-oxo-1-phenyl-2,5-dihydro-1H-pyrrole-3-carboxylate (5d &
50d)
J ¼ 7.1 Hz, 3H). 13C NMR (101 MHz, DMSO‑d6)
d (A): 167.9, 163.1,
161.3, 160.4, 158.6, 145.8, 139.4, 139.1, 137.7, 135.0, 131.8, 129.1, 128.9
(2C), 128.5 (2C), 127.9 (q, J ¼ 32.1 Hz), 126.9 (2C), 125.4 (q, J ¼ 3.8 Hz,
2C), 123.9 (q, J ¼ 272.1 Hz), 123.5, 121.5, 115.6, 115.1, 114.6, 102.9,
White solid, 47%, mp 212e214ꢀС (toluene, ethyl acetate); IR
n
,
71.6, 60.5, 39.3, 29.1, 13.1.19
F
NMR (377 MHz, CDCl3)
cmꢁ1: 3482, 3288, 3240, 3156, 3105 (NH2, OH), 2242 (CN), 1716,
1705, 1689, 1668, 1652, 1617. After crystallization dr ~11.5 : 1 (A: B).
d
(A þ B): ꢁ60.86 (s, A), ꢁ60.96 (s, B). Anal. calcd for C33H25F3N4O6:
C, 62.86; H, 4.00; N, 8.89. Found: C, 63.22; H, 4.18; N, 9.13.
1H NMR (400 MHz, DMSO‑d6)
d
(A þ B): [10.81 (s, A), 9.71 (s, B),
S1H], 8.24 (br. s, 0.08H, B), [8.10 (dd, J ¼ 8.1, 1.5 Hz, A), 8.06 (dd,
J ¼ 8.0, 1.5 Hz, B), S1H], 7.81e7.55 (m, 7.76H), 7.45 (d, J ¼ 8.7 Hz,
0.16H, B), 7.38e7.29 (m, 4H), [6.98e6.92 (m, A), 6.68e6.64 (m, B),
S2H], [5.44 (s, A), 5.14 (s, B), S1H], [3.64 (s, B), 3.62 (s, A), S3H], [3.47
4.9.8. Ethyl 2-(2-amino-1-cyano-2-oxoethyl)-4-(4-hydroxy-1-
methyl-2-oxo-1,2-dihydroquinolin-3-yl)-2-(4-nitrophenyl)-5-oxo-
1-phenyl-2,5-dihydro-1H-pyrrole-3-carboxylate (5h & 50h)
Yellow solid, 49%, mp 188e191ꢀС (acetone). After crystallization
(s, B), 3.41 (s, A), S3H]. 13C NMR (101 MHz, DMSO‑d6)
d
(A): 167.7,
dr ~5 : 1 (A: B). 1H NMR (400 MHz, DMSO‑d6)
d
(A þ B): [10.77 (br. s,
162.9, 162.0, 160.4, 158.6, 145.4, 139.4, 138.2, 134.7, 134.2, 133.6,
131.9, 129.1 (2C), 128.6 (2C), 128.5 (2C), 128.5 (2C), 128.1, 123.6,
121.6,115.5,114.9,114.7,103.0, 71.4, 51.7, 40.1, 29.2. HRMS (ESIþ): m/
z [M þ H]þ calcd for C31H23ClN4O6: 583.1379; found: 583.1380.
A), 9.80 (br. s, B), S1H], 8.38 (d, J ¼ 8.4 Hz, 1.84H), 8.23 (s, 0.16H, B),
8.14e7.67 (m, 6H), 7.63e7.56 (m, 1H), 7.40e7.25 (m, 4H), [6.97 (dd,
J ¼ 6.9, 2.8 Hz, A), 6.76e6.69 (m, B), S2H], [5.49 (s, A), 5.22 (s, B),
S1H], 4.02e3.77 (m, 2H), [3.65 (s, B), 3.62 (s, A), S3H], 0.78 (t,
J ¼ 7.1 Hz, 3H). 13C NMR (101 MHz, DMSO‑d6)
d (A): 167.7, 162.7,
4.9.5. Ethyl 2-(2-amino-1-cyano-2-oxoethyl)-4-(4-hydroxy-2-oxo-
1-phenyl-1,2-dihydroquinolin-3-yl)-5-oxo-1,2-diphenyl-2,5-
dihydro-1H-pyrrole-3-carboxylate (5e & 50e)
161.2, 160.4, 158.5, 147.6, 145.0, 142.8, 139.4, 139.1, 134.6, 131.9, 128.7
(4C), 128.4 (2C), 128.2, 123.7 (2C), 123.5, 121.6, 115.5, 114.8, 114.7,
103.1, 71.3, 60.5, 40.0, 29.1, 13.0. Anal. calcd for C32H25N5O8: C,
63.26; H, 4.15; N, 11.53. Found: C, 63.40; H, 4.17; N, 11.41.
The compound was purified by column chromatography
(tolueneeEtOAc ¼ 1:1, Rf 0.29) followed by crystallization, yellow
solid, 48%, mp 210e211ꢀС (toluene, EtOAc); IR
n
, cmꢁ1: 3449, 3313,
4.9.9. Ethyl 2-(2-amino-1-cyano-2-oxoethyl)-1-(4-chlorophenyl)-
4-(4-hydroxy-2-oxo-2H-chromen-3-yl)-5-oxo-2-phenyl-2,5-
dihydro-1H-pyrrole-3-carboxylate (6 & 60)
3169 (NH2, ОН), 2243 (CN), 1710, 1646, 1610. After crystallization dr
~24 : 1 (A: B). 1H NMR (400 MHz, DMSO‑d6)
d
(A þ B): [10.87 (s, A),
9.75 (s, B), S1H], [8.30 (br. s, B), 7.78 (br. s, A), S2H], [8.14 (dd, J ¼ 8.1,
1.5 Hz, A), 8.09 (dd, J ¼ 8.0, 1.6 Hz, B), S1H], 7.67e7.40 (m, 9H),
7.33e7.22 (m, 6H), 6.97e6.92 (m, 2H), [6.65e6.61 (m, B), 6.58 (dd,
J ¼ 8.6, 1.0 Hz, A), S1H], [5.44 (s, A), 5.13 (s, B), S1H], 4.07e3.83 (m,
Yellow solid, 53%, mp 208e211ꢀС (toluene, ethanol); IR , cmꢁ1
n :
3471, 3358, 3331, 3247 (NH2, ОН), 2241 (CN), 1705, 1698, 1679, 1651,
1618, 1610. After crystallization dr ~9 : 1 (A: B). 1H NMR (400 MHz,
DMSO‑d6)
d
(A þ B): 11.82 (br. s, 1H), [8.08 (dd, J ¼ 8.0, 1.6 Hz, A),
2H), 0.85 (t, J ¼ 7.1 Hz, 3H). 13C NMR (101 MHz, DMSO‑d6)
d
(A):
8.04 (dd, J ¼ 8.0, 1.6 Hz, B), S1H], 7.94 (s, 0.1H, B), 7.79e7.30 (m,
11.9H), [7.02e6.94 (m, A), 6.70e6.63 (m, B), S2H], [5.46 (s, A), 5.17
(s, B), S1H], 4.08e3.81 (m, 2H), [0.84 (t, J ¼ 7.1 Hz, B), 0.83 (t,
168.0, 163.2, 161.3, 160.4, 159.0, 146.0, 140.2, 137.7, 137.6, 135.0,
134.9, 131.5, 129.9 (2C), 129.1, 129.1, 128.8, 128.6 (2C), 128.5, 128.3
(4C), 128.0,127.0 (2C),123.4,121.9, 115.4 (2C),115.0,103.4, 71.7, 60.5,
39.6, 13.3. HRMS (ESIþ): m/z [M þ H]þ calcd for C37H28N4O6:
625.2082; found: 625.2084.
J ¼ 7.1 Hz, A), overlapped, S3H]. 13C NMR (101 MHz, DMSO‑d6)
d (A):
d
167.3, 162.8, 162.7, 161.1, 159.7, 152.6, 145.7, 136.8, 134.8, 134.1,
133.2, 132.4, 130.0 (2C), 129.1, 128.9 (2C), 128.4 (2C), 126.8 (2C),
124.2, 123.7, 116.5, 115.5, 115.0, 97.0, 71.5, 60.7, 38.6, 13.2. HRMS
(ESIþ): m/z [M þ Na]þ calcd for C31H22ClN3O7: 606.1038; found:
606.1037.
4.9.6. Ethyl 2-(2-amino-1-cyano-2-oxoethyl)-1-(4-chlorophenyl)-
4-(4-hydroxy-2-oxo-1-phenyl-1,2-dihydroquinolin-3-yl)-5-oxo-2-
phenyl-2,5-dihydro-1H-pyrrole-3-carboxylate (5f & 50f)
Yellow solid, 58%, mp 202e204ꢀС (toluene, EtOAc); IR
n
, cmꢁ1
:
4.9.10. Ethyl 2-(2-amino-1-cyano-2-oxoethyl)-1-(4-chlorophenyl)-
4-(4-hydroxy-2-oxo-2,5-dihydrofuran-3-yl)-5-oxo-2-phenyl-2,5-
dihydro-1H-pyrrole-3-carboxylate (7 & 70)
3439, 3313, 3172 (NH2, ОН), 2242 (CN), 1711, 1704, 1650, 1614. After
crystallization dr ~100 : 1 (A: B). 1H NMR (400 MHz, DMSO‑d6)
d
(A þ B): [10.89 (s, A), 9.84 (s, B), S1H], 8.14 (dd, J ¼ 8.1, 1.5 Hz, 1H),
Yellow solid, 63%, mp 214e215ꢀС (acetone, ethanol); IR , cmꢁ1
n :
7.74 (br. s, 2H), 7.66e7.43 (m, 9H), 7.38e7.24 (m, 5H), 7.02e6.94 (m,
2H), [6.63 (d, J ¼ 8.8 Hz, B), 6.58 (dd, J ¼ 8.5,1.0 Hz, A), S1H], [5.49 (s,
3484, 3425, 3381, 3312, 3245, 3177 (NH2, OH), 2246 (CN), 1728,
1703, 1694, 1668, 1651, 1609. After crystallization dr > 99 : 1 (A: B).
A), 5.16 (s, B), S1H], 4.07e3.82 (m, 2H), 0.85 (t, J ¼ 7.1 Hz, 3H). 13
C
1H NMR (400 MHz, DMSO‑d6)
d (A): 13.06 (br. s, 1H), 7.58 (br. s, 1H),
NMR (101 MHz, DMSO‑d6)
d
(A): 167.9, 163.1, 161.3, 160.3, 159.1,
7.56 (br. s, 1H), 7.55e7.45 (m, 5H), 7.36e7.31 (m, 2H), 7.03e6.98 (m,
2H), 5.41 (s, 1H), 4.86 (d, J ¼ 16.7 Hz, 1H), 4.80 (d, J ¼ 16.7 Hz, 1H),
4.00e3.85 (m, 2H), 0.94 (t, J ¼ 7.1 Hz, 3H). 13C NMR (101 MHz,
145.9, 140.2, 137.6, 137.5, 134.8, 134.0, 132.4, 131.5, 130.0 (2C), 129.9
(2C),129.1 (2C),129.0,128.8 (2C),128.5,128.4 (2C),126.9 (2C),123.5,
121.9,115.4 (2C),115.0,103.3, 71.6, 60.6, 39.1,13.3. HRMS (ESIþ): m/z
[M þ H]þ calcd for C37H27ClN4O6: 659.1692; found: 659.1701.
DMSO‑d6)
d (A): 178.0, 170.5, 168.1, 162.5, 161.6, 142.4, 134.5, 134.0,
132.4, 132.3, 130.0 (2C), 129.2, 128.9 (2C), 128.3 (2C), 126.7 (2C),
114.8, 91.8, 71.9, 67.2, 60.7, 37.6, 13.3. Anal. calcd for C26H20ClN3O7:
C, 59.84; H, 3.86; N, 8.05. Found: C, 59.69; H, 4.22; N, 7.80.
4.9.7. Ethyl 2-(2-amino-1-cyano-2-oxoethyl)-4-(4-hydroxy-1-
methyl-2-oxo-1,2-dihydroquinolin-3-yl)-5-oxo-2-phenyl-1-(4-
(trifluoromethyl)phenyl)-2,5-dihydro-1H-pyrrole-3-carboxylate (5g
& 50g)
4.9.11. Ethyl 2-(2-amino-1-cyano-2-oxoethyl)-4-(3-hydroxy-1,4-
dioxo-1,4-dihydronaphthalen-2-yl)-5-oxo-1,2-diphenyl-2,5-
dihydro-1H-pyrrole-3-carboxylate (8a & 80a)
The compound was purified by column chromatography
(tolueneeEtOAc ¼ 1:2, Rf 0.35) followed by crystallization, yellow
solid, 61%, mp 208e211ꢀС (acetone, hexane). After crystallization dr
Yellow solid, 37%, mp 223e225ꢀС (acetone); IR , cmꢁ1: 3658,
n
3317, 3462, 3355, 3354, 3292, 3193 (OH, NH2), 2248 (CN), 1716,
~5 : 1 (A: B). 1H NMR (400 MHz, DMSO‑d6)
d
(A þ B): [10.62 (br. s, A),
1683, 1674, 1660, 1628. After crystallization dr > 99 : 1 (A: B). 1H
9.62 (br. s, B), S1H], [8.23 (br. s, B), 8.03 (br. s, B), 7.77 (br. s, A), S2H],
8.13e8.05 (m, 1H), 7.74e7.47 (m, 9H), 7.39e7.28 (m, 1H), [7.21 (d,
J ¼ 8.3 Hz, A), 6.90 (d, J ¼ 8.3 Hz, B), S2H], [5.58 (s, A), 5.22 (s, B),
S1H], 4.01e3.76 (m, 2H), [3.64 (s, B), 3.61 (s, A), S3H], 0.77 (t,
NMR (400 MHz, DMSO‑d6)
d
(A): 12.04 (br. s, 1H), 8.10 (d, J ¼ 7.4 Hz,
1H), 8.05 (d, J ¼ 7.5 Hz, 1H), 7.90 (dt, J ¼ 20.5, 7.4 Hz, 2H), 7.78 (br. s,
1H), 7.66 (br. s,1H), 7.61e7.42 (m, 5H), 7.32e7.21 (m, 3H), 6.93e6.85
(m, 2H), 5.34 (s, 1H), 3.96e3.77 (m, 2H), 0.76 (t, J ¼ 7.1 Hz, 3H). 13
C
9