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F. Palacios et al. / Tetrahedron 61 (2005) 2779–2794
(m), 165.3. 19F NMR (282 MHz, CDCl3) d: K75.2 (dd,
C17H13F4N3O2 (367): C, 55.59; H, 3.57; N, 11.44. Found:
C, 55.48; H, 3.38; N, 11.31. 1H NMR (400 MHz, CDCl3) for
E-isomer of 18b, d: 1.28 (d, JZ7.0 Hz, 6H), 3.02 (dq, JZ
7.0 Hz, 1H), 7.50 (s, 1H), 7.51 (d, JZ8.8 Hz, 2H), 8.30 (d,
3
2
3JFFZ15 Hz, JHFZ6 Hz), K190.0 (dq, JHFZ45 Hz,
3JFFZ15 Hz). MS (EI) m/z 367 (MC, 3). Anal. Calcd for
C25H19F4NO2 (367): C, 62.12; H, 4.66; N, 3.81. Found: C,
61.99; H, 4.70; N, 3.83.
1
JZ8.8 Hz, 2H), 9.59 (s, 1H). H NMR (400 MHz, CDCl3)
for Z-isomer of 18b, d: 1.18 (d, JZ6.8 Hz, 6H), 3.05 (dq,
JZ6.8 Hz, 1H), 7.46 (d, JZ8.7 Hz, 2H), 7.50 (s, 1H), 8.26
(d, JZ8.7 Hz, 2H), 9.82 (s, 1H). 1H NMR (400 MHz,
CDCl3) for 28a, d: 4.51 (s, 1H), 5.19 (bs, 2H).
4.7.10. Reaction of 2-azadiene (6c) with enamine (9c).
4.7.10.1. 2-Ethoxycarbonyl-6-(1,2,2,3,3,4,4,5,5,6,6,7,
7,7-tetradecafluoro-heptyl)-3,4-trimethylen-5-phenyl-
pyridine (24b). The general procedure was followed using
(1E,3E)-1-ethoxycarbonyl-4-phenyl-3-perfluorohepthyl-2-
azabuta-1,3-diene 6c obtained in situ and 1-cyclopent-1-
enylpyrrolidine 9c (0.67 g) in CHCl3 at room temperature
for 15 h. Chromatographic separation (15/1, hexane/ethyl
acetate) gave 1.76 g (56%) of 24b as a colorless oil; RfZ
0.43 (1/5, ethyl acetate/hexane). IR (KBr) n 1724,
4.7.12. Reaction of 2-azadiene (6i) with enamine (9b).
4.7.12.1. 5-Isopropyl-6-(4-nitrophenyl)-2-perfluoro-
hepthyl-3-cyanopiridine (25b), 5-isopropyl-6-(4-nitro-
phenyl)-2-(1,2,2,3,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-
hepthyl)-3-cyanopiridine (26b) and 3-isopropyl-2-(4-
nitrophenyl)-6-perfluorohepthyl-1,2-dihydro-5-cyano-
piridine (27b). The general procedure was followed using
(1E,3Z)-4-cyano-1-(4-nitrophenyl)-3-perfluorohepthyl-2-
azabuta-1,3-diene (6i) obtained in situ and and trans
3-methyl-1-pyrrolidylbut-1-ene 9b (0.67 g) in CHCl3 at
room temperature for 5 h. Chromatographic separation
(10/1, hexane/ethyl acetate) gave 1.11 g (35%) of 25b as
an orange solid; mp 80–81 8C (CH2Cl2/hexane); 0.56 g
(18%) of 26b as a yellow solid; mp 93–94 8C (CH2Cl2/
hexane); 0.68 g (22%) of 27b as a yellow solid; mp 90–
91 8C (ethyl acetate/hexane) 0.03 g (3%) of 18b (see
reaction of 2-azadiene 6h with enamine 9b) and 0.15 g
(7%) of 28b as a white solid mp 127–128 8C (hexane/ethyl
1
1224 cmK1. H NMR (400 MHz, CDCl3) d: 1.46 (t, JZ
7.1 Hz, 3H), 2.08–2.18 (m, 2H), 2.71–2.76 (m, 2H), 3.41–
3.48 (m, 2H), 4.44–4.55 (m, 2H), 5.83–5.99 (m, 1H), 7.18–
7.51 (m, 5H). 13C NMR (100 MHz, CDCl3) d: 14.2, 24.3,
32.4, 33.1, 61.6, 82.5–85.0 (m), 107.0–120.2 (m), 128.1–
156.6 (m), 165.4. 19F NMR (282 MHz, CDCl3) d: K81.2,
K117.1 to K126.6 (m). MS (EI) m/z 617 (MC, 2). Anal.
Calcd for C24H17F14NO2 (617): C, 46.69; H, 2.78; N, 2.27.
Found: C, 46.73; H, 2.81; N, 2.25.
4.7.11. Reaction of 2-azadiene (6h) with enamine (9b).
4.7.11.1. 5-Isopropyl-6-(4-nitrophenyl)-2-perfluoro-
ethyl-3-cyanopiridine (25a) and 5-isopropyl-6-(4-nitro-
phenyl)-2-(1,2,2,2-tetrafluoroethyl)-3-cyanopiridine
(26a). The general procedure was followed using (1E,3Z)-4-
cyano-1-(4-nitrophenyl)-3-perfluoroethyl-2-azabuta-1,3-
diene (6h) obtained in situ and trans 3-methyl-1-pyrro-
lidylbut-1-ene 9b (0.67 g) in CHCl3 at room temperature for
3 h. Chromatographic separation (15/1, hexane/ethyl
acetate) gave 0.78 g (40%) of 25a as a white solid; mp
120–121 8C (ethyl acetate/hexane); 0.33 g (18%) of 26a as
an orange oil, RfZ0.50 (1/5, ethyl acetate/hexane); 0.04 g
(4%) of E-18b as yellow oil, RfZ0.27 (1/5, ethyl acetate/
hexane); 0.03 g (3%) of Z-18b and as a orange oil, RfZ0.45
(1/5, ethyl acetate/hexane) and 0.06 g (6%) of 28a as an
orange solid; mp 69–70 8C (ethyl acetate/hexane). Data for
1
acetate). Data for 25b: IR (KBr) n 2233, 1523 cmK1. H
NMR (300 MHz, CDCl3) d: 1.30 (d, JZ6.9 Hz, 6H), 3.25
(dq, JZ6.9 Hz, 1H), 7.68 (d, JZ8.8 Hz, 2H), 8.23 (s, 1H),
8.38 (d, JZ8.8 Hz, 2H). 13C NMR (75 MHz, CDCl3) d:
23.6, 29.7, 109.2, 110.2–111.1 (m), 113.9, 123.8, 130.1,
141.6, 143.4, 145.6, 145.7–146.4 (m), 148.5, 158.4. 19F
NMR (282 MHz, CDCl3) d: K81.0, K110.8 to K126.3
(m). MS (EI) m/z 635 (MC, 20). Anal. Calcd for
C22H12F15N3O2 (635): C, 41.59; H, 1.90; N, 6.61. Found:
C, 41.31; H, 1.91; N, 6.79. Data for 26b: IR (KBr) n 2235,
1
1524 cmK1. H NMR (300 MHz, CDCl3) d: 1.29 (d, JZ
6.7 Hz, 3H), 1.30 (d, JZ6.7 Hz, 3H), 3.21 (dq, JZ6.7 Hz,
1H), 6.20 (dd, 1JHFZ24.9 Hz, 3JHFZ19.1 Hz, 1H), 7.66 (d,
JZ8.8 Hz, 2H), 8.18 (s, 1H), 8.37 (d, JZ8.8 Hz, 2H). 13C
1
25a: IR (KBr) n 2237, 1520 cmK1. H NMR (400 MHz,
1
NMR (75 MHz, CDCl3) d: 23.6, 29.2, 87.3 (dt, JCF
Z
CDCl3) d: 1.30 (d, JZ6.8 Hz, 6H), 3.26 (dq, JZ6.8 Hz,
1H), 7.68 (d, JZ8.7 Hz, 2H), 8.24 (s, 1H), 8.38 (d, JZ
8.7 Hz, 2H). 13C NMR (100 MHz, CDCl3) d: 23.6, 29.2,
108.6, 110.9 (tq, 1JCFZ258 Hz, 2JCFZ39 Hz), 113.8, 118.5
2
195 Hz, JCFZ23 Hz), 109.8, 110.2–111.2 (m), 114.5,
123.7, 123.7, 130.0, 140.7, 143.1–143.6 (m), 144.0, 144.2,
148.3, 158.6. 19F NMR (282 MHz, CDCl3) d: K81.1,
3
1
2
K110.8 (t, JFFZ13.7 Hz), K120.8 to K126.4 (m),
(tq, JCFZ287 Hz, JCFZ36 Hz), 123.8, 130.1, 141.7,
143.4, 145.6, 145.8–146.4 (m), 148.5, 158.2. 19F NMR
(282 MHz, CDCl3) d: K82.4, K113.3. MS (EI) m/z 385
(MC, 23). Anal. Calcd for C17H12F5N3O2 (385): C, 52.99;
H, 3.14; N, 10.91. Found: C, 52.48; H, 3.31; N, 10.81. Data
for 26a: IR (KBr) n 2236, 1522 cmK1. 1H NMR (400 MHz,
CDCl3) d: 1.26 (d, JZ7.1 Hz, 3H), 1.28 (d, JZ7.0 Hz, 3H),
3
K198.6 (d, JFFZ13.7 Hz). MS (CI) m/z 618 (MCC1,
100). Anal. Calcd for C22H13F14N3O2 (617): C, 42.80; H,
2.12; N, 6.81. Found: C, 42.77; H, 2.09; N, 6.85. Data for
27b: IR (KBr) n 3284, 2214, 1531 cmK1 1H NMR
.
(300 MHz, CDCl3) d: 1.00 (d, JZ6.8 Hz, 3H), 1.05 (d,
JZ6.7 Hz, 3H), 2.07 (dq, JZ6.8, 6.7 Hz, 1H), 5.25 (s, 1H),
5.33 (d, JZ3.3 Hz, 1H), 6.08 (s, 1H), 7.50 (d, JZ8.7 Hz,
2H), 8.26 (d, JZ8.8 Hz, 2H). 13C NMR (75 MHz, CDCl3)
d: 20.7, 21.2, 31.6, 57.1, 83.8, 109.8–110.9 (m), 116.0,
116.6, 124.4, 128.0, 137.6, 143.5–144.2 (m), 147.4, 148.3.
19F NMR (282 MHz, CDCl3) d: K81.1, K112.7 to K126.4
(m). MS (CI) m/z 638 (MCC1, 100). Anal. Calcd for
C22H14F15N3O2 (637): C, 41.46; H, 2.21; N, 6.59. Found: C,
2
3.20 (dq, JZ7.0, 7.1 Hz, 1H), 5.97 (dq, JHFZ44.3 Hz,
3JHFZ6.0 Hz, 1H), 7.66 (d, JZ8.8 Hz, 2H), 8.16 (s, 1H),
8.37 (d, JZ8.8 Hz, 2H). 13C NMR (100 MHz, CDCl3) d:
1
2
23.6, 23.7, 29.2, 87.8 (dq, JCFZ194 Hz, JCFZ35 Hz),
1
2
109.2, 114.5, 121.5 (dq, JCFZ283 Hz, JCFZ28 Hz),
123.7, 130.0, 140.6, 143.9, 144.2, 148.3, 158.6. 19F NMR
3
3
(282 MHz, CDCl3) d: K76.6 (dd, JFFZ12.5 Hz, JHF
Z
1
2
3
41.41; H, 2.26; N, 6.57. H NMR (400 MHz, CDCl3) for
28b, d: 4.56 (s, 1H), 5.30 (bs, 2H).
6.0 Hz), K197.9 (dq, JHFZ44.3 Hz, JFFZ12.5 Hz). MS
(CI, 80V) m/z 368 (MCC1, 100). Anal. Calcd for