Molecules 2017, 22, 2035
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(3aS,6aR)-Ethyl
5-(4-ethylphenyl)-2-methyl-4,6-dioxo-1-phenetyl-1,3a,4,5,6,6a-hexahydropyrrolo[3,4-b]
pyrrole-3-carboxylate 8c. 0.70 g; yield 82%; m.p. 147–149 ◦C; 1H NMR (DMSO-d6),
δ (ppm): 1.18 (3H, t,
J = 7.1 Hz, 4-CH3CH2C6H4); 1.20 (3H, t, J = 7.6 Hz, CH3CH2O); 2.07 (3H, s, CH3-Het); 2.64 (2H, q,
J = 7.1 Hz, 4-CH3CH2C6H4); 2.80–2.87 (1H, m, CH2CH2Ph); 2.92–2.99 (1H, m, CH2CH2Ph); 3.60–3.70
(2H, m, CH2CH2Ph); 3.96–4.10 (2H, m, CH3CH2O); 4.28 (1H, dd, J = 10.5 Hz, J = 1.1 Hz, H-6a); 4.75
(1H, d, J = 10.5 Hz, H-3a); 7.14–7.17 (2H, m, CHarom); 7.21–7.26 (3H, m, CHarom); 7.30–7.34 (4H, m,
CHarom); 13C NMR (DMSO-d6),
δ (ppm): 11.98, 14.90, 15.84, 28.21, 33.53, 46.93, 47.62, 58.43, 63.67, 92.92,
126.81, 127.25, 128.63, 128.88, 129.25, 130.24, 139.14, 144.54, 161.61, 165.30, 174.33, 175.75; HRMS-ESI,
m/z ([M + H]+), calcd for C26H28N2O4+H+ 433.2123, found 433.2128.
X-Ray Crystallographic data for 8c. CCDC 1574386 contains the supplementary crystallographic data for
html (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44-1223-336033; E-mail:
deposit@ccdc.cam.ac.uk). Crystal data for C26H28N2O4 (M = 432.50 g/mol): monoclinic, space group
P 21/n (no. 14), a = 15.0252(9) Å, b = 8.6768(5) Å, c = 17.3436(10) Å,
V = 2240.3(2) Å3, Z = 4, T =120(2) K, (CuK
) = 0.087 mm-1, Dcalc = 1.282 g/cm3. 20916 reflections
α β γ
= 90◦, = 97.7760(10)◦, = 90◦
µ
α
◦
◦
measured (4.74
≤ Θ ≤ 51.992 ), 4387 unique (Rint = 0.0380, Rsigma = 0.0411) which were used in all
2
calculations. The final R1 was 0.0483 (I > 2σ(I)) and wR2 was 0.0817 (all data).
(3aS,6aR)-Ethyl 5-(4-ethoxyphenyl)-2-methyl-4,6-dioxo-1-phenetyl-1,3a,4,5,6,6a-hexahydropyrrolo[3,4-b]
pyrrole-3-carboxylate 8d. 0.66 g; yield 73%; m.p. 164–166 ◦C; 1H NMR (DMSO-d6),
δ
(ppm): 1.20 (3H, t,
J = 7.0 Hz, CH3CH2O); 1.34 (3H, t, J = 7.0 Hz, 4-CH3CH2OC6H4); 2.06 (3H, s, CH -Het); 2.78–2.87
(1H, m, CH2CH2Ph); 2.91–2.96 (1H, m, CH2CH2Ph); 3.60–3.69 (2H, m, CH2CH2Ph); 4.04–4.12 (4H, m,
2CH3CH2); 4.27 (1H, br.d, J = 10.5 Hz, H-6a); 4.74 (1H, d, J = 10.5 Hz, H-3a); 7.01 (2H, d, J = 8.7 Hz
CHarom); 7.15 (2H, d, J = 8.7 Hz, CHarom); 7.23–7.26 (3H, m, CHarom); 7.30–7.33 (2H, m, CHarom);
13C NMR (DMSO-d6),
(ppm): 11.97, 14.91, 14.96, 33.53, 46.91, 47.54, 58.42, 63.59, 63.70, 92.91, 114.96,
3
,
δ
124.99, 126.81, 128.58, 128.88, 129.25, 139.15, 158.63, 161.58, 165.31, 174.42, 175.86; HRMS-ESI, m/z ([M
+ H]+), calcd. for C26H28N2O5 + H+ 449.2073, found 449.2067.
(3aS,6aR)-Ethyl 1-benzyl-2-methyl-4,6-dioxo-5-(3,4-dichlorophenyl)-1,3a,4,5,6,6a-hexahydropyrrolo[3,4-b]
◦
1
pyrrole-3-carboxylate 8e. 0.64 g; yield 70%; m.p. 146–147 C; H NMR (DMSO-d6),
δ (ppm): 1.20
(3H, t, J = 7.1 Hz, CH3CH2O); 2.31 (3H, s, CH3-Het); 4.00–4.14 (2H, m, CH3CH2O); 4.33 (1H, br.d,
J = 10.5 Hz, H-6a); 4.52 (1H, d, J = 10.5 Hz, H-3a); 4.59 (1H, d, J = 16.7 Hz, CH2Ph); 4.78 (1H, d, J =
16.7 Hz, CH2Ph); 7.25 (2H, d, J = 7.4 Hz, CHarom); 7.30–7.34 (2H, m, CHarom); 7.40 (2H, t, J = 7.5 Hz,
CHarom); 7.61 (1H, d, J = 2.3 Hz, CHarom); 7.79 (1H, d, J = 8.6 Hz, CHarom); 13C NMR (DMSO-d6),
δ
(ppm): 12.48, 14.90, 47.74, 48.12, 58.60, 63.15, 93.12, 127.49, 127.75, 127.87, 129.19, 129.27, 131.30,
131.53, 131.61, 132.52, 136.76, 161.61, 165.29, 173.27, 175.11; HRMS-ESI, m/z ([M + H]+), calcd for
C23H20Cl2N2O4 + H+ 459.0874, found 459.0868.
(3aS,6aR)-Ethyl 5-(3,4-dichlorophenyl)-2-methyl-4,6-dioxo-1-phenetyl-1,3a,4,5,6,6a-hexahydropyrrolo[3,4-b]
pyrrole-3-carboxylate 8f. 0.65 g; yield 69%; m.p. 155–156 ◦C; 1H NMR (DMSO-d6),
δ
(ppm): 1.18 (3H,
t, J = 7.1 Hz, CH3CH2O); 2.08 (3H, s, CH3-Het); 2.81–2.88 (1H, m, CH2CH2Ph); 2.93–2.99 (1H, m,
CH2C 2Ph); 3.60–3.67 (2H, m, C 2CH2Ph); 3.98–4.10 (2H, m, CH3C 2); 4.28 (1H, dd, J = 10.6 Hz, J =
1.0 Hz, H-6a); 4.75 (1H, d, J = 10.6 Hz, H-3a); 7.22–7.27 (3H, m, CHarom); 7.30–7.35 (3H, m, CHarom); 7.64
(1H, d, J = 2.3 Hz, CHarom); 7.79 (1H, d, J = 8.6 Hz, CHarom); 13C NMR (DMSO-d6),
(ppm): 12.05, 14.91,
H
H
H
δ
14.96, 33.48, 46.81, 47.74, 58.45, 63.56, 92.63, 126.82, 127.83, 128.88, 129.01, 129.25, 129.32, 131.31, 131.53,
131.60, 132.58, 139.14, 161.80, 165.23, 173.69, 175.14; HRMS, m/z ([M + H]+), calcd for C24H22Cl2N2O4
+ H+ 473.1031, found 473.1024.
4. Conclusions
Herein, we presented the new unusual variant of the realization of the Hantzsch-type synthetic
scheme C–C + C–C–N for the synthesis of polyhydrogenated pyrrolo[3,4-b]pyrroles based on the