3200
J.D. Waetzig et al. / Tetrahedron 65 (2009) 3197–3201
0.020 mmol) and potassium tert-butoxide (0.0045 g, 0.04 mmol)
were added successively to the solution. The reaction mixture was
stirred at 23 ꢁC for 24 h. Purification was performed using silica gel
chromatography (10:1 hexane/EtOAc) affording 3b as a colorless oil
56.1, 45.9, 36.7, 29.4; IR (thin film, cmꢂ1) 3074, 3004, 2904, 2279,
1606, 1517; HRMS (TOF MS ESþ) m/z calculated for C15H16N2O2
279.1110, [MþNa]þ found 279.1115; TLC Rf¼0.2 (3:1 hexanes/
EtOAc).
(36 mg, 79%). 1H NMR (CDCl3, 400 MHz)
d
7.28 (ad, J¼7.5 Hz, 2H),
6.94 (ad, J¼8.7 Hz, 2H), 5.67 (dddd, J¼16.5,14.1, 7.8, 6.2 Hz,1H), 5.25
(dd, J¼17.1, 1.3 Hz, 1H), 5.18 (ad, J¼10.3 Hz, 1H), 3.99 (d, J¼5.5 Hz,
1H), 3.83 (s, 3H), 3.26 (ddd, J¼7.7, 7.6, 5.6 Hz, 1H), 2.79–2.69 (m,
4.2.8. 2-Allyl-2-(1-(3,4-dimethoxyphenyl)but-3-enyl)-
malononitrile (4e)
1H NMR (CDCl3, 400 MHz)
d 6.92–6.84 (m, 3H), 5.94–5.85 (m,
2H); 13C NMR (CDCl3, 125 MHz)
d
160.2, 133.4, 129.3, 128.4, 120.0,
1H), 5.56–5.47 (m, 1H), 5.41 (ad, J¼9.9 Hz, 1H), 5.41 (ad, J¼16.8 Hz,
1H), 5.10 (ad, J¼17.0 Hz, 1H), 5.00 (ad, J¼10.0 Hz, 1H), 3.91 (s, 3H),
3.90 (s, 3H), 3.03 (dd, J¼11.6, 4.0 Hz, 1H), 2.92–2.81 (m, 2H), 2.50
(dd, J¼14.1, 7.3 Hz, 1H), 2.40 (dd, J¼13.9, 7.1 Hz, 1H); 13C NMR
114.8, 112.3, 111.8, 55.5, 45.5, 36.7, 29.5; IR (thin film, cmꢂ1) 298,
2838, 2254, 1612, 1515; HRMS (TOF MS ESþ) m/z calculated for
C14H14N2O 249.1004, [MþNa]þ found 249.1002; TLC Rf¼0.2 (3:1
hexanes/EtOAc).
(CDCl3, 125 MHz)
d 149.4, 149.4, 133.6, 128.9, 127.2, 123.1, 121.9,
118.4, 115.5, 114.6, 111.2, 111.2, 56.0, 55.9, 51.0, 43.3, 40.5, 36.3; IR
(thin film, cmꢂ1) 3083, 3004, 2838, 2246, 1643, 1517; HRMS (TOF
MS APCIþ) m/z calculated for C18H20N2O2 319.1422, [MþNa]þ found
319.1419; TLC Rf¼0.3 (3:1 hexane/EtOAc).
4.2.2. 2-(1-Phenylbut-3-enyl)malononitrile (3a)
1H NMR (CDCl3, 400 MHz)
d 7.40–7.25 (m, 5H), 5.70–5.60 (m,
1H), 5.23 (d, J¼17.0 Hz,1H), 5.17 (d, J¼10.2 Hz,1H), 4.01 (d, J¼5.6 Hz,
1H), 3.29 (m, 1H), 2.75 (m, 2H). The spectral values obtained were
consistent with those reported in the literature.19
4.2.9. (E)-2-(1-Phenylhexa-1,5-dien-3-yl)malononitrile (3f)
1H NMR (CDCl3, 400 MHz)
d
7.42 (d, J¼7.3 Hz, 2H), 7.36 (dd,
4.2.3. 2-Allyl-2-(1-(4-methoxyphenyl)but-3-enyl)
malononitrile (3b)
J¼7.8, 7.1 Hz, 2H), 7.32 (d, J¼7.2 Hz, 1H), 6.71 (d, J¼15.8 Hz, 1H), 6.10
(dd, J¼15.8, 8.9 Hz, 1H), 5.81–5.71 (m, 1H), 5.28 (ad, J¼17.0 Hz, 1H),
5.24 (d, J¼10.1 Hz, 1H), 3.90 (d, J¼4.9 Hz, 1H), 2.98–2.90 (m, 1H),
1H NMR (CDCl3, 500 MHz)
d
7.28 (d, J¼9.3 Hz, 2H), 6.94 (d,
J¼7.0 Hz, 2H), 5.95–5.83 (m, 1H), 5.55–5.45 (m, 1H), 5.40 (dd, J¼8.1,
0.6 Hz, 1H), 5.32 (dd, J¼13.6, 0.9 Hz, 1H), 5.08 (dd, J¼13.6, 1.2 Hz,
1H), 4.98 (dd, J¼9.2, 1.0 Hz, 1H), 3.93 (s, 3H), 3.05 (dd, J¼9.3, 3.2 Hz,
1H), 2.95–2.84 (m, 2H), 2.50 (dd, J¼11.1, 5.9 Hz,1H), 2.40 (dd, J¼11.2,
5.7 Hz, 1H). Analytical data is consistent with the reported litera-
ture values.20
2.60–2.48 (m, 2H); 13C NMR (CDCl3, 125 MHz)
d 136.3, 135.7, 132.9,
128.9, 128.8, 127.0, 124.2, 112.2, 111.4, 44.3, 36.8, 27.9; IR (thin film,
cmꢂ1) 3083, 2908, 2254, 1643, 1494; HRMS (TOF MS ESþ) m/z cal-
culated for C15H14N2 245.1055, [MþNa]þ found 245.1054; TLC
Rf¼0.3 (3:1 hexanes/EtOAc).
4.2.10. 2-(1-(Furan-2-yl)but-3-enyl)malononitrile (3g)
4.2.4. 2-(1-p-Tolylbut-3-enyl)malononitrile (3c)
1H NMR (CDCl3, 400 MHz)
d
7.45 (t, J¼1.4 Hz, 1H), 6.40 (d,
1H NMR (CDCl3, 400 MHz)
d
7.26–7.16 (m, 4H), 5.68 (dddd,
J¼1.5 Hz, 2H), 5.72 (dddd, J¼16.9, 9.4, 7.7, 6.5 Hz, 1H), 5.28 (dd,
J¼17.1, 1.3 Hz, 1H), 5.22 (dd, J¼10.1, 1.1 Hz, 1H), 4.08 (d, J¼5.9 Hz,
1H), 3.49 (ddd, J¼7.3, 7.3, 1.0 Hz, 1H), 2.80–2.67 (m, 2H); 13C NMR
J¼16.9 10.6, 7.6, 6.4 Hz, 1H), 5.25 (dd, J¼17.1, 1.4 Hz, 1H), 5.18 (ad,
J¼10.3 Hz, 1H), 4.00 (d, J¼5.7 Hz, 1H), 3.26 (ddd, J¼7.7, 7.6, 5.7 Hz,
1H), 2.80–2.68 (m, 2H), 2.38 (s, 3H); 13C NMR (CDCl3, 125 MHz)
(CDCl3, 125 MHz)
d 149.7, 143.5, 132.6, 120.5, 111.7, 111.4, 110.9,
d
139.1, 133.5, 133.4, 130.1, 128.0, 120.0, 112.2, 111.8, 45.8, 36.6, 29.3,
109.4, 40.2, 35.3, 27.4; IR (thin film, cmꢂ1) 3083, 2921, 2248, 1642;
21.3; IR (thin film, cmꢂ1) 3081, 2921, 2254, 1643, 1515; HRMS (TOF
MS ESþ) m/z calculated for C14H14N2 233.1055, [MþNa]þ found
233.1055; TLC Rf¼0.3 (3:1 hexanes/EtOAc).
TLC Rf¼0.6 (3:1 hexanes/EtOAc).
4.2.11. 2-Allyl-2-(1-(furan-2-yl)but-3-enyl)malononitrile (4g)
1H NMR (CDCl3, 500 MHz)
d
7.45 (t, J¼1.3 Hz, 1H), 6.40 (d,
4.2.5. 2-Allyl-2-(1-p-tolylbut-3-enyl)malononitrile (4c)
J¼1.4 Hz, 2H), 5.90 (dddd, J¼17.3, 10.3, 7.2, 7.2 Hz, 1H), 5.60 (dddd,
J¼16.9, 10.2, 6.8, 6.8 Hz, 1H), 5.43 (dd, J¼10.2, 1.0 Hz, 1H), 5.38
(dd, J¼16.8, 1.2 Hz, 1H), 5.13 (ddd, J¼17.0, 2.8, 1.4 Hz, 1H), 5.06 (ddd,
J¼10.2, 2.5, 1.1 Hz, 1H), 3.31 (dd, J¼9.9, 5.7 Hz, 1H), 2.90–2.80 (m,
2H), 2.59–2.44 (m, 2H); Analytical data is consistent with the
reported literature values.20
1H NMR (CDCl3, 400 MHz)
d 7.24–7.19 (m, 4H), 5.89 (dddd,
J¼16.9 10.6, 7.6, 6.4 Hz, 1H), 5.68 (dddd, J¼16.9 10.6, 7.6, 6.4 Hz, 1H),
5.25 (dd, J¼17.1, 1.4 Hz, 1H), 5.18 (ad, J¼10.3 Hz, 1H), 4.00 (d,
J¼5.7 Hz, 1H), 3.26 (ddd, J¼7.7, 7.6, 5.7 Hz, 1H), 2.80–2.68 (m, 2H),
2.38 (s, 3H); 13C NMR (CDCl3, 125 MHz)
d 139.1, 133.8, 132.0, 130.0,
129.1, 129.0, 123.3, 118.6, 115.6, 114.7, 51.1, 43.5, 40.7, 36.4; IR (thin
film, cmꢂ1) 3083, 2983, 2925, 2246, 1643; HRMS (TOF MS ESþ) m/z
calculated for C17H18N2 273.1368, [MþNa]þ found 273.1367; TLC
Rf¼0.4 (3:1 hexanes/EtOAc).
4.2.12. 2-(1-(Pyridin-3-yl)but-3-enyl)malononitrile (3h)
1H NMR (CDCl3, 500 MHz)
d
8.67 (d, J¼4.0 Hz, 1H), 8.62 (s, 1H),
7.74 (ad, J¼7.82 Hz, 1H), 7.39 (dd, J¼8.1, 4.9 Hz, 1H), 5.71–5.62 (m,
1H), 5.28 (ad, J¼17.0 Hz, 1H), 5.23 (ad, J¼10.0 Hz, 1H), 4.09 (d,
J¼5.4 Hz, 1H), 3.36 (ddd, J¼7.7, 7.6, 5.6 Hz, 1H), 2.84–2.71 (m, 2H);
4.2.6. 2-(1-(4-Bromophenyl)but-3-enyl)malononitrile (3d)
1H NMR (CDCl3, 400 MHz)
d
7.57 (d, J¼8.5 Hz, 2H), 7.24 (d,
13C NMR (CDCl3, 125 MHz)
d 150.7, 149.9, 135.4, 132.4, 132.2, 124.2,
J¼8.3 Hz, 2H), 5.66 (dddd, J¼16.5, 10.5, 7.8, 6.4 Hz, 1H), 5.25 (dd,
J¼17.0, 1.4 Hz, 1H), 5.21 (dd, J¼10.5, 1.3 Hz, 1H), 4.02 (d, J¼5.5 Hz,
1H), 3.27 (ddd, J¼7.6, 7.6, 5.6 Hz, 1H), 2.80–2.66 (m, 2H); 13C NMR
121.0, 111.7, 111.2, 43.7, 36.31, 29.8; IR (thin film, cmꢂ1) 3083, 2908,
2254, 1543, 1577; HRMS (TOF MS ESþ) m/z calculated for C12H11N3
220.0851, [MþNa]þ found 220.0853; TLC Rf¼0.2 (1:1 hexane/
EtOAc).
(CDCl3, 125 MHz)
d 135.4, 132.8, 132.6, 129.8, 123.4, 120.5, 111.9,
111.4, 45.5, 36.5, 28.9; IR (thin film, cmꢂ1) 3081, 2904, 2360, 2256,
1643; TLC Rf¼0.3 (3:1 hexanes/EtOAc).
4.2.13. 2-(1-Cyclohexylbut-3-enyl)malononitrile (3i)
1H NMR (CDCl3, 400 MHz)
d
5.76 (dddd, J¼17.1, 10.2, 8.6, 6.0 Hz,
4.2.7. 2-(1-(3,4-Dimethoxyphenyl)but-3-enyl)malononitrile (3e)
1H), 5.28 (dd, J¼17.0, 1.3 Hz, 1H), 5.23 (d, J¼10.0 Hz, 1H), 3.91 (d,
J¼4.2 Hz, 1H), 2.57–2.50 (m, 1H), 2.31–2.23 (m, 1H), 1.96–1.86 (m,
2H), 1.85–1.65 (m, 4H), 1.36–1.04 (m, 6H); 13C NMR (CDCl3,
1H NMR (CDCl3, 400 MHz)
d 6.90 (s, 2H), 6.86 (s, 1H), 5.73–5.64
(m, 1H), 5.26 (d, J¼17.1 Hz, 1H), 5.19 (d, J¼10.3 Hz, 1H), 4.01 (d,
J¼5.3 Hz, 1H), 3.91 (s, 3H), 3.90 (s, 3H), 3.25 (ddd, J¼7.7, 7.6, 5.4 Hz,
125 MHz) d 134.3,120.2,112.9,112.6, 45.4, 39.9, 33.7, 31.2, 29.7, 26.5,
1H), 2.74 (at, J¼7.6 Hz, 2H); 13C NMR (CDCl3, 125 MHz)
d
149.7,
26.3, 26.2, 24.7; IR (thin film, cmꢂ1) 2931, 2360, 1642, 1448; TLC
149.5, 133.4, 128.9, 120.5, 120.1, 112.3, 111.8, 111.6, 111.0, 56.2,
Rf¼0.8 (3:1 hexanes/EtOAc).