M.-L. Bennasar et al. / Tetrahedron 58 (2002) 8099–8106
8103
calcd for C19H18Cl3NO5: C, 51.09; H, 4.06; N, 3.14. Found:
C, 51.51; H, 4.25; N, 2.98.
1H NMR (300 MHz) d 3.57 (s, 3H, OMe), 5.63 (q, J¼2 Hz,
1H, 4-H), 6.10 (s, 1H, CHPh2), 7.20–7.45 (m, 15H, 2-H,
Ph), 7.88 (s, 1H, 6-H); 13C NMR (75.4 MHz) d 34.3 (C-4),
51.4 (OMe), 71.3 (CHPh2), 95.6 (CCl3), 107.3 (C-3), 112.4
(C-5), 126.9, 127.0, 128.2, 128.5, 128.8, 128.9, 129.2,
129.3, 130.7, 131.5 (CH, Ph), 136.5 (C-2), 137.0 (C, Ph),
137.2 (C, Ph), 142.5 (C-6), 144.0 (C, Ph), 166.5, 178.5
(CO). Anal. calcd for C29H21Cl3F3NO3: C, 58.56; H, 3.56;
N, 2.35. Found: C, 59.00; H, 3.93; N, 2.54.
3.6.8. 4-[3-(Ethoxycarbonyl)phenyl]-3-(methoxycar-
bonyl)-1-methyl-5-(trichloroacetyl)-1,4-dihydropyridine
(4e). Elution with 87:13 hexanes–AcOEt; 1H NMR
(200 MHz, from a 7:1 mixture of 4e and 3e) d 1.37 (t,
J¼7.2 Hz, 3H, CH3), 3.40 (s, 3H, NMe), 3.66 (s, 3H, OMe),
4.34 (q, J¼7 Hz, 2H, OCH2), 5.07 (s, 1H, 4-H), 7.19 (d,
J¼1.2 Hz, 1H, 2-H), 7.37 (t, J¼7.5 Hz, 1H, Ph), 7.62 (m,
1H, Ph), 7.84 (m, 1H, Ph), 7.86 (d, J¼1 Hz, 1H, 6-H), 7.98
(s, 1H, Ph).
3.7.2. 1-Benzhydryl-4-(2-chlorophenyl)-3-(methoxycar-
bonyl)-5-(trichloroacetyl)-1,4-dihydropyridine
(10c).
1
Elution with 95:5 hexanes–AcOEt; H NMR (300 MHz) d
3.57 (s, 3H, OMe), 5.43 (s, 1H, 4-H), 6.04 (s, 1H, CHPh2),
7.05 (m, 1H, Ph), 7.15 (m, 1H, Ph), 7.20–7.45 (m, 13H,
2-H, Ph), 7.89 (s, 1H, 6-H); 13C NMR (75.4 MHz) d 36.6
(C-4), 51.4 (OMe), 71.3 (CHPh2), 95.7 (CCl3), 105.8 (C-3),
110.9 (C-5), 126.5, 127.8, 128.1, 128.6, 128.7, 128.9, 129.2,
131.5 (CH, Ph), 133.6 (C–Cl), 136.6 (C-2), 137.1 (C, Ph),
137.2 (C, Ph), 142.0 (C, Ph), 142.9 (C-6), 166.3, 178.6
(CO); HRMS calcd for C28H21NO3Cl4 559.0275, found
559.0265.
3.6.9. 5-(Methoxycarbonyl)-1-methyl-3-(trichloro-
acetyl)-2-[(2-trifluoromethyl)phenyl]-1,2-dihydropyri-
dine (5b). Elution with 9:1 hexanes–AcOEt; mp 1588C; 1H
NMR (300 MHz) d 3.09 (s, 3H, NMe), 3.80 (s, 3H, OMe),
6.08 (s, 1H, 2-H), 7.44 (dd, J¼7.5, 7.8 Hz, 1H, Ph), 7.56 (dd,
J¼7.5, 7.8 Hz, 1H, Ph), 7.67 (d, J¼8.1 Hz, 1H, Ph), 7.71 (s,
1H, 4-H), 7.84 (d, J¼8.1 Hz, 1H, Ph), 8.50 (s, 1H, 6-H); 13C
NMR (75.4 MHz) d 43.3 (NMe), 51.3 (OMe), 58.0 (C-2),
95.4 (CCl3), 96.0 (C-5), 110.4 (C-3), 124.2 (q, J¼265 Hz,
CF3), 126.0 (CH, Ph), 127.0 (q, J¼30 Hz, C–CF3), 129.1
(CH, Ph), 130.1 (CH, Ph), 133.1 (CH, Ph), 139.2 (C-4),
152.0 (C-6), 165.3, 177.8 (CO). Anal. calcd for C17H13Cl3-
F3NO3: C, 46.13; H, 2.96; N, 3.16. Found: C, 46.20; H, 2.97;
N, 3.28.
3.7.3. 1-Benzhydryl-4-[2-(ethoxycarbonyl)phenyl]-3-
(methoxycarbonyl)-5-(trichloroacetyl)-1,4-dihydropyri-
dine (10d). Elution with 88:12 hexanes–AcOEt; mp 1408C;
1H NMR (300 MHz) d 1.45 (t, J¼7.2 Hz, 3H, CH3), 3.54 (s,
3H, OMe), 4.45 (m, 2H, OCH2), 6.01 (s, 1H, CHPh2), 6.20
(s, 1H, 4-H), 7.20–7.50 (m, 14H, 2-H, Ph), 7.75 (d, J¼8 Hz,
1H, Ph), 7.86 (d, J¼1.2 Hz, 1H, 6-H); 13C NMR (75.4 MHz)
d 14.3 (CH2), 33.4 (C-4), 51.4 (OMe), 60.8 (OCH2), 71.1
(CHPh2), 95.8 (CCl3), 107.1 (C-3), 112.4 (C-5), 126.2,
128.2, 128.4, 128.7, 128.8, 129.1, 129.4, 129.7 (CH, Ph),
130.6 (C, Ph), 131.4 (CH, Ph), 136.3 (C-2), 137.1 (C, Ph),
137.4 (C, Ph), 142.4 (C-6), 145.8 (C, Ph), 166.3, 167.7,
178.3 (CO). Anal. calcd for C31H26Cl3NO5: C, 62.17; H,
4.38; N, 2.34. Found: C, 62.09; H, 4.51; N, 2.23.
3.6.10. 2-(2-Chlorophenyl)-5-(methoxycarbonyl)-1-
methyl-3-(trichloroacetyl)-1,2-dihydropyridine
(5c).
Elution with 9:1 hexanes–AcOEt; mp 1758C; 1H NMR
(300 MHz) d 3.14 (s, 3H, NMe), 3.79 (s, 3H, OMe), 6.19 (s,
1H, 2-H), 7.25 (m, 2H, Ph), 7.39 (dd, J¼1.2, 7.8 Hz, 1H,
Ph), 7.60 (dd, J¼2, 7.4 Hz, 1H, Ph), 7.67 (s, 1H, 4-H), 8.50
(d, J¼1.5 Hz, 1H, 6-H); 13C NMR (75.4 MHz) d 42.8
(NMe), 51.3 (OMe), 58.6 (C-2), 95.4 (CCl3), 96.2 (C-5),
109.6 (C-3), 128.1 (CH, Ph), 129.3 (CH, Ph), 129.7 (CH,
Ph), 130.1 (CH, Ph), 132.4 (C–Cl), 137.4 (C, Ph), 139.4
(C-4), 151.7 (C-6), 165.4, 177.9 (CO). Anal. calcd for
C16H13Cl4NO3: C, 46.98; H, 3.20; N, 3.42. Found: C, 47.19;
H, 3.18; N, 3.42.
3.7.4. 1-Benzhydryl-4-[3-(ethoxycarbonyl)phenyl]-3-
(methoxycarbonyl)-5-(trichloroacetyl)-1,4-dihydropyri-
dine (10e). Elution with 3:7 hexanes–CH2Cl2; mp 1308C;
1H NMR (300 MHz) d 1.39 (t, J¼7.5 Hz, 3H, CH3), 3.62 (s,
3H, OMe), 4.38 (dq, J¼1.5, 7.2 Hz, 2H, OCH2), 5.10 (s, 1H,
4-H), 6.06 (s, 1H, CHPh2), 7.25–7.45 (m, 12H, 2-H, Ph),
7.60 (d, J¼7.8 Hz, 1H, Ph), 7.86 (d, J¼7.6 Hz, 1H, Ph), 7.90
(s, 1H, 6-H), 8.07 (s, 1H, Ph); 13C NMR (75.4 MHz) d 14.4
(CH2), 37.7 (C-4), 51.6 (OMe), 60.8 (OCH2), 71.3 (CHPh2),
95.6 (CCl3), 105.9 (C-3), 111.6 (C-5), 128.0, 128.4, 128.8,
128.9, 129.3 (CH, Ph), 130.6 (C, Ph), 132.9 (CH, Ph), 136.3
(C-2), 137.0 (C, Ph), 137.5 (C, Ph), 142.7 (C-6), 145.4 (C, Ph),
166.3, 166.5, 178.8 (CO). Anal. calcd for C31H26Cl3NO5: C,
62.17; H, 4.38; N, 2.34. Found: C, 61.98; H, 4.51; N, 2.45.
3.6.11. 2-[(2-Ethoxycarbonyl)phenyl]-5-(methoxycar-
bonyl)-1-methyl-3-(trichloroacetyl)-1,2-dihydropyridine
(5d). Elution with 92:8 hexanes–AcOEt; mp 122–1238C;
1H NMR (300 MHz) d 1.47 (t, J¼7.2 Hz, 3H, CH3), 3.19 (s,
3H, NMe), 3.80 (s, 3H, OMe), 4.49 (m, 2H, OCH2), 6.77 (s,
1H, 2-H), 7.34 (dt, J¼1.5, 7.6 Hz, 1H, Ph), 7.49 (dt, J¼1.5,
7.4 Hz, 1H, Ph), 7.76 (s, 1H, 4-H), 7.80 (m, 2H, Ph), 8.38 (d,
J¼1.2 Hz, 1H, 6-H); 13C NMR (75.4 MHz) d 14.3 (CH3),
43.0 (NMe), 51.4 (OMe), 57.2 (C-2), 61.5 (OCH2), 95.6
(C-5, CCl3), 111.2 (C-3), 128.5 (C, Ph), 129.0 (2CH, Ph),
129.9 (C, Ph), 132.8 (CH, Ph), 138.8 (C-4), 141.5 (C, Ph),
152.4 (C-6), 165.6, 167.4, 177.8 (CO). Anal. calcd for
C19H18Cl3NO5: C, 51.09; H, 4.06; N, 3.14. Found: C, 51.20;
H, 4.15; N, 2.92.
3.7.5. 1-Benzhydryl-3-(methoxycarbonyl)-4-[2-[2-(meth-
oxycarbonyl)vinyl]phenyl]-5-(trichloroacetyl)-1,4-di-
hydropyridine (10f). Elution with 8:2 hexanes–AcOEt; 1H
NMR (300 MHz) d 3.54 (s, 3H, OMe), 3.82 (s, 3H, OMe),
5.36 (s, 1H, 4-H), 6.06 (s, 1H, CHPh2), 6.39 (d, J¼15.6 Hz,
1H, CHvCH–CO2), 7.10–7.50 (m, 15H, 2-H, Ph), 7.90 (s,
1H, 6-H), 8.71 (d, J¼15.6 Hz, 1H, CHvCH–CO2); 13C
NMR (50.3 MHz) d 34.2 (C-4), 51.4 (OMe), 51.7 (OMe),
71.3 (CHPh2), 95.6 (CCl3), 107.1 (C-3), 112.3 (C-5), 119.5
(CHvCH–CO2), 126.1, 127.0, 128.2, 128.6, 128.8, 129.0,
3.7. Analytical data of (trichloroacetyl)dihydropyridines
10 of Table 2
3.7.1. 1-Benzhydryl-3-(methoxycarbonyl)-5-(trichloro-
acetyl)-4-[2-(trifluoromethyl)phenyl]-1,4-dihydropyri-
dine (10b). Elution with 93:7 hexanes–AcOEt; mp 808C;