G
S. Saranya et al.
Paper
Synthesis
Rf = 0.36 (EtOAc/hexane, 3:7).
1H NMR (500 MHz, CDCl3): δ = 7.34–7.27 (m, 4 H), 7.26–7.17 (m, 1 H),
6.41 (d, J = 16 Hz, 1 H), 6.20 (m, 1 H), 5.92 (br s, 1 H), 5.76 (dd, J1 = 6
Hz, J2 = 2.5 Hz, 1 H), 5.63 (m, 1 H), 4.65 (br s, 1 H), 3.55 (br s, 1 H),
2.65–2.61 (m, 1 H), 2.52–2.49 (m, 1 H), 1.48–1.41 (m, 18 H).
13C NMR (125 MHz, CDCl3): δ = 156.7, 155.0, 135.4, 132.8, 130.5,
130.0, 128.5, 128.3, 128.2, 127.7, 126.1, 121.5, 81.4, 80.3, 53.2, 49.8,
31.2, 28.2, 28.1, 28.1.
IR (neat): 3299, 3057, 2984, 2928, 2362, 2334, 1709, 1471, 1413,
1378, 1306, 1235, 1173, 1128, 1099, 1059, 862, 759, 700, 658, 614,
537 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.33 (d, J = 7.5 Hz, 2 H), 7.28–7.25 (m, 2
H), 7.19–7.16 (m, 1 H), 6.47–6.41 (m, 2 H), 6.22–6.18 (m, 1 H), 5.77–
5.74 (m, 1 H), 5.63 (dd, J1 = 4 Hz, J2 = 2 Hz, 1 H), 4.71–4.70 (m, 1 H),
4.23–4.14 (m, 4 H), 3.58 (br s, 1 H), 2.67–2.62 (m, 1 H), 2.53–2.50 (m,
1 H), 1.30–1.20 (m, 6 H).
HRMS (ESI): m/z [M + Na]+ calcd for C23H32N2NaO4: 423.22598; found:
423.20526.
13C NMR (125 MHz, CDCl3): δ = 156.8, 156.2, 137.3, 134.4, 131.9,
131.2, 130.3, 129.8, 128.5, 127.1, 126.2, 125.6, 64.8, 62.6, 62.2, 51.4,
35.1, 14.5.
Diethyl 1-(5-Styrylspiro[2.4]hept-6-en-4-yl)hydrazine-1,2-dicar-
boxylate (3ea)
HRMS (ESI): m/z [M + Na]+ calcd for C19H24N2NaO4: 367.16338; found:
367.16383.
Yield: Method A: 35 mg (50%); Method B: 33 mg (47%); pale yellow,
viscous liquid.
Rf = 0.44 (EtOAc/hexane, 3:7).
Diisopropyl 1-(2-Styrylcyclopent-3-enyl)hydrazine-1,2-dicarbox-
ylate (3ba)
IR (neat): 3293, 3058, 2982, 2927, 2854, 1711, 1602, 1517, 1467,
1447, 1411, 1380, 1301, 1230, 1173, 1129, 1097, 1061, 1023, 970,
Yield: Method A: 48 mg (70%); Method B: 44 mg (63%); pale yellow,
viscous liquid.
924, 873, 759, 696 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.37 (d, J = 7.5 Hz, 2 H), 7.31–7.28 (m, 2
H), 7.22–7.20 (m, 1 H), 6.49–6.46 (m, 1 H), 6.32–6.28 (m, 1 H), 6.15 (br
s, 1 H), 5.66 (s, 1 H), 5.31 (d, J = 5.5 Hz, 1 H), 4.50 (br s, 1 H), 4.24–4.18
(m, 4 H), 3.82 (m, 1 H), 1.31–1.24 (m, 6 H), 0.89–0.87 (m, 1 H), 0.81–
0.79 (m, 3 H).
13C NMR (125 MHz, CDCl3): δ = 156.0, 154.2, 136.3, 131.2, 129.9,
129.0, 128.8, 128.6, 128.4, 128.2, 127.1, 126.2, 68.4, 62.4, 61.9, 52.7,
29.7, 14.5, 14.2, 9.0, 8.9.
Rf = 0.48 (EtOAc/hexane, 3:7).
IR (neat): 3299, 3059, 2982, 2933, 1712, 1495, 1460, 1407, 1381,
1307, 1250, 1179, 1141, 1107, 1039, 965, 918, 841, 761, 700, 649 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7. 33 (d, J = 7.5 Hz, 2 H), 7.30–7.26 (m,
2 H), 7.20–7.17 (m, 1 H), 6.44–6.41 (m, 1 H), 6.28 (m, 1 H), 6.21 (br s, 1
H), 5.77–5.75 (m, 1 H), 5.64–5.63 (m, 1 H), 4.99–4.89 (m, 2 H), 4.70 (br
s, 1 H), 3.58 (br s, 1 H), 2.63 (m, 1 H), 2.53–2.50 (m, 1 H), 1.29–1.20
(m, 12 H).
HRMS (ESI): m/z [M + Na]+ calcd for C21H26N2NaO4: 393.17903; found:
393.17748.
13C NMR (125 MHz, CDCl3): δ = 155.1, 154.1, 138.9, 135.2, 134.3,
134.0, 130.6, 130.3, 128.8, 128.5, 128.4, 128.1, 126.1, 70.0, 69.2, 65.1,
47.9, 35.1, 22.1, 22.0, 21.9.
HRMS (ESI): m/z [M + Na]+ calcd for C21H28N2NaO4: 395.19468; found:
395.19540.
Diisopropyl 1-(5-Styrylspiro[2.4]hept-6-en-4-yl)hydrazine-1,2-di-
carboxylate (3fa)
Yield: Method A: 36 mg (53%); Method B: 36 mg (53%); pale yellow,
viscous liquid.
Rf = 0.53 (EtOAc/hexane, 3:7).
Dibenzyl 1-(2-Styrylcyclopent-3-enyl)hydrazine-1,2-dicarboxylate
(3ca)
IR (neat): 3289, 3058, 3025, 2982, 2852, 1710, 1600, 1572, 1494,
1467, 1451, 1404, 1382, 1299, 1235, 1180, 1144, 1108, 1035, 966,
Yield: Method A: 32 mg (49%); Method B: 31 mg (48%); pale yellow,
viscous liquid.
835, 758, 696, 604, 564 cm–1
.
Rf = 0.46 (EtOAc/hexane, 3:7).
1H NMR (500 MHz, CDCl3): δ = 7.36–7.32 (m, 3 H), 7.21–7.19 (m, 2 H),
6.48–6.44 (m, 1 H), 6.31 (br s, 1 H), 6.21 (s, 1 H), 5.65 (s, 1 H), 5.29 (d,
J = 5 Hz, 1 H), 4.97–4.89 (m, 2 H), 4.49–4.30 (m, 1 H), 3.81–3.74 (m, 1
H), 1.28–1.22 (m, 12 H), 0.90–0.87 (m, 1 H), 0.79–0.78 (m, 3 H).
13C NMR (125 MHz, CDCl3): δ = 156.2, 155.8, 137.4, 136.3, 131.3,
129.7, 128.8, 128.5, 128.4, 127.0, 126.2, 117.9, 70.2, 70.0, 69.4, 52.3,
29.6, 22.0, 21.9, 14.1, 13.9.
IR (neat): 3296, 3061, 3032, 2958, 2926, 2854, 1955, 1714, 1606,
1496, 1452, 1406, 1303, 1262, 1215, 1162, 1125, 1050, 970, 912, 849,
823, 748, 697, 594 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.33–7.27 (m, 10 H), 7.24–7.18 (m, 5
H), 6.50–6.40 (m, 2 H), 6.18 (br s, 1 H), 5.74 (s, 1 H), 5.62 (s, 1 H), 5.20–
5.08 (m, 4 H), 4.75 (br s, 1 H), 3.58 (br s, 1 H), 2.65 (m, 1 H), 2.35 (m, 1
H).
HRMS (ESI): m/z [M + Na]+ calcd for C23H30N2NaO4: 421.21033; found:
421.20918.
13C NMR (125 MHz, CDCl3): δ = 156.5, 155.8, 137.2, 136.4, 135.8,
135.5, 134.5, 132.0, 130.9, 130.5, 128.5, 128.4, 128.4, 128.4, 128.1,
128.0, 127.8, 127.1, 126.2, 126.0, 123.4, 68.1, 67.8, 63.0, 51.4, 35.0.
HRMS (ESI): m/z [M + Na]+ calcd for C29H28N2NaO4: 491.19468; found:
491.19562.
Diethyl 1-(2-(4-Chlorostyryl)cyclopent-3-enyl)hydrazine-1,2-di-
carboxylate (3ab)
Yield: Method A: 48 mg (61%); Method B: 43 mg (54%); pale yellow,
viscous liquid.
Rf = 0.38 (EtOAc/hexane, 3:7).
Di-tert-butyl 1-(2-Styrylcyclopent-3-enyl)hydrazine-1,2-dicarbox-
ylate (3da)
IR (neat): 3296, 2983, 2935, 1712, 1594, 1489, 1411, 1378, 1310,
Yield: Method A: 35 mg (52%); Method B: 28 mg (42%); pale yellow,
viscous liquid.
1261, 1176, 1095, 1060, 1019, 892, 840, 764, 647 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.31–7.22 (m, 4 H), 6.47–6.37 (m, 2 H),
6.21–6.17 (m, 1 H), 5.76 (dd, J1 = 6 Hz, J2 = 2.5 Hz, 1 H), 5.62 (d, J = 4
Hz, 1 H), 4.70 (br s, 1 H), 4.22–4.14 (m, 4 H), 3.58 (br s, 1 H), 2.66–2.61
(m, 1 H), 2.52–2.49 (m, 1 H), 1.30–1.20 (m, 6 H).
Rf = 0.58 (EtOAc/hexane, 3:7).
IR (neat): 3410, 3065, 2978, 2925, 2854, 1705, 1613, 1479, 1455,
1395, 1368, 1334, 1252, 1158, 1051, 1023, 850, 757, 699 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–I